Herbicidal compounds and compositions

ABSTRACT

The invention concerns novel compounds of the formula I ##STR1## wherein: W are selected from alkyl, alkenyl and alkynyl; 
     X are selected from halogen, nitro, cyano, alkyl, substituted alkyl, hydroxy, alkoxy, substituted alkoxy, alkenyl, alkynyl, alkenyloxy, alkynyloxy, acyloxy, alkoxycarbonyl, alkylthio, alkylsulfinyl, alkylsulfonyl, sulfamoyl, substituted sulfamoyl, amino, substituted amino, and the groups formyl and alkanoyl and the oxime, imine and Schiff base derivatives thereof, and an alkylene group which bridges two adjacent carbon atoms of the benzene ring; 
     R 1  is selected from hydrogen, alkyl, alkenyl, alkynyl, substituted alkyl, alkylsulfonyl, arylsulfonyl, acyl and an inorganic or organic cation; 
     R 2  is selected from alkyl, substituted alkyl, alkenyl, haloalkenyl, alkynyl and haloalkynyl; 
     R 3  is selected from alkyl, fluoroalkyl, alkenyl, alkynyl, and phenyl; 
     p is zero or an integer selected from 1 to 4; 
     n is zero or an integer selected from 1 to 3; and 
     m is zero or an integer selected from 1 to 3. 
     The compounds of the invention show cereal selective herbicidal properties and plant growth regulating properties and in further embodiments the invention provides processes for the preparation of the compounds of formula I, intermediates useful in the preparation of the compounds of formula I, compositions containing as active ingredient a compound of formula I, and herbicidal and plant growth regulating processes utilizing compounds of formula I.

This is a division of application Ser. No. 06/461,003, filed Jan. 26,1983 now U.S. Pat. No. 4,952,722.

This invention relates to organic compounds having biological activityand in particular to organic compounds having herbicidal properties andplant growth regulating properties, to processes for the preparation ofsuch compounds, to intermediates useful in the preparation of suchcompounds and to herbicidal compositions and processes utilizing suchcompounds and to plant growth regulating compositions and processesusing such compounds.

The use of certain cyclohexane-1,3-dione derivatives as grass herbicidesis known in the art. For example, the "Pesticide Manual" (C R WorthingEditor, The British Crop Protection Council, 6th Edition 1979) describesthe cyclohexane-1,3-dione derivative known commercially asalloxydim-sodium (methyl3-[1-allyloxyimino)butyl]-4-hydroxy-6,6-dimethyl-2-oxocyclohex-3-ene-carboxylate)and its use as a grass herbicide. This compound is disclosed inAustralian Patent No 464 655 and its equivalents such as UK Patent No 1461 170 and U.S. Pat. No. 3,950,420.

More recently, at the 1980 British Crop Protection Conference ("1980British Crop Protection Conference--Weeds, Proceedings Vol 1, ResearchReports", pp 39 to 46, British Crop Protection Council, 1980), a newcyclohexane-1,3-dione grass herbicide code named NP 55(2-(N-ethoxybutrimidoyl)-5-(2-ethylthiopropyl)-3-hydroxy-2-cyclohexen-1-one)was announced. This compound is disclosed in Australian PatentApplication No AU-Al-35,314/78 and its equivalents.

As indicated above, both alloxydim-sodium and NP 55 are grassherbicides, that is, herbicides which selectively control the growth ofgrass weeds (monocotyledonous plants) in broad-leaved crops(dicotyledonous plants).

At the 1978 International Union of Pure and Applied Chemistry FourthInternational Congress of Pesticide Chemistry ("Advances in PesticideScience--Part 2", pp 235-243, Pergamon Press, 1979), in a paperdiscussing the chemical structure and herbicidal activity ofalloxydim-sodium, Iwataki and Hirono made the following disclosure aboutthe herbicidal selectivity between wheat and oats of certain 5-phenylsubstituted cyclohexane-1,3-dione derivatives: "When substituted phenylgroups were introduced at the C-5 position (Table 6), the selectivitybetween wheats and oats such as Avena fatua and Avena sativa wasobserved. The selectivity was found only in the case ofpara-substituents at the phenyl nucleus and the effect was not found inthe case of di- or tri- substitution. Even in the para-substituents, thedegree of activity or selectivity was different. The best result wasobtained when the methyl group was introduced at the para-position andthe hydroxy or the methoxy derivative gave moderately good results."

It has now been found that certain novel 5-aryl substitutedcyclohexan-1,3-dione derivatives exhibit particularly useful cerealselective herbicidal activity and plant growth regulating activity.

Accordingly the invention provides a compound of formula I: ##STR2##wherein: W, which may be the same or different, are selected from thegroup consisting of C₁ to C₆ alkyl, C₂ to C₆ alkenyl and C₂ to C₆alkynyl;

X, which may be the same or different, are selected from the groupconsisting of: halogen; nitro; cyano; C₁ to C₆ alkyl; C₁ to C₆ alkylsubstituted with a substituent selected from the group consisting ofhalogen, nitro, hydroxy, C₁ to C₆ alkoxy and C₁ to C₆ alkylthio; C₂ toC₆ alkenyl; C₂ to C₆ alkynyl; hydroxy; C₁ to C₆ alkoxy; C₁ to C₆ alkoxysubstituted with a substituent selected from halogen and C₁ to C₆alkoxy; C₂ to C₆ alkenyloxy; C₂ to C₆ alkynyloxy; C₂ to C₆ alkanoyloxy;(C₁ to C₆ alkoxy) carbonyl; C₁ to C₆ alkylthio; C₁ to C₆ alkylsulfinyl;C₁ to C₆ alkylsulfonyl; sulfamoyl; N-(C₁ to C₆ alkyl)sulfamoyl;N,N-di(C₁ to C₆ alkyl)sulfamoyl; benzyloxy; substituted benzyloxywherein the benzene ring is substituted with from one to threesubstituents selected from the group consisting of halogen, nitro, C₁ toC₆ alkyl, C₁ to C₆ alkoxy and C₁ to C₆ haloalkyl; the group NR⁸ R⁹wherein R⁸ and R⁹ are independently selected from the group consistingof hydrogen, C₁ to C₆ alkyl, C₂ to C₆ alkanoyl, benzoyl and benzyl; thegroups formyl and C₂ to C₆ alkanoyl and the oxime, imine and Schiff basederivatives thereof; and the group --(CH₂)_(q) -- which bridges twoadjacent carbon atoms of the benzene ring and wherein q is an integerselected from 2 to 5;

R¹ is chosen from the group consisting of: hydrogen; C₁ to C₆ alkyl; C₂to C₆ alkenyl; C₂ to C₆ alkynyl; substituted C₁ to C₆ alkyl wherein thealkyl group is substituted with a substituent chosen from the groupconsisting of C₁ to C₆ alkoxy, C₁ to C₆ alkylthio, phenyl andsubstituted phenyl wherein the benzene ring is substituted with from oneto three substituents chosen from the group consisting of halogen,nitro, cyano, C₁ to C₆ alkyl, C₁ to C₆ haloalkyl, C₁ to C₆ alkoxy and C₁to C₆ alkylthio; C₁ to C₆ (alkyl) sulfonyl; benzenesulfonyl; substitutedbenzenesulfonyl wherein the benzene ring is substituted with from one tothree substituents chosen from the group consisting of halogen, nitro,cyano, C₁ to C₆ alkyl, C₁ to C₆ haloalkyl, C₁ to C₆ alkoxy and C₁ to C₆alkylthio; an acyl group; and an inorganic or organic cation;

R² is chosen from the group consisting of: C₁ to C₆ alkyl; C₂ to C₆alkenyl; C₂ to C₆ haloalkenyl; C₂ to C₆ alkynyl; C₂ to C₆ haloalkynyl;substituted C₁ to C₆ alkyl wherein the alkyl group is substituted with asubstituent chosen from the group consisting of halogen, C₁ to C₆alkoxy, C₁ to C₆ alkylthio, phenyl and substituted phenyl wherein thebenzene ring is substituted with from one to three substituents chosenfrom the group consisting of halogen, nitro, cyano, C₁ to C₆ alkyl, C₁to C₆ haloalkyl, C₁ to C₆ alkoxy and C₁ to C₆ alkylthio;

R³ is chosen from the group consisting of: C₁ to C₆ alkyl; C₁ to C₆fluoroalkyl; C₂ to C₆ alkenyl; C₂ to C₆ alkynyl; and phenyl;

p is zero or an integer chosen from 1 to 4;

n is zero or an integer chosen from 1 to 3; and

m is zero or an integer chosen from 1 to 3.

When in the compound of formula I X is chosen from the group formyl andC₂ to C₆ alkanoyl and the oxime, and imine (Schiff base) derivativesthereof, the nature of the oxime and imine derivatives is not narrowlycritical. Although not intending to be bound by theory, it is believedthat in the plant the (substituted) imine group may be removed to givethe corresponding compound of formula I in which X is formyl or C₂ to C₆alkanoyl. Suitable values for the groups formyl and C₂ to C₆ alkanoyland the oxime, imine and Schiff base derivatives thereof include groupsof the formula --C(R¹⁰)═NR¹¹ wherein R¹⁰ is chosen from hydrogen and C₁to C₅ alkyl and R¹¹ is chosen from hydrogen, C₁ to C₆ alkyl, phenyl,benzyl, hydroxy, C₁ to C₆ alkoxy, phenoxy and benzyloxy.

When in the compound of formula I R¹ is chosen from acyl the nature ofthe acyl group is not narrowly critical. Although not intending to bebound by theory, it is believed that when R¹ is acyl the acyl group maybe removed in the plant by hydrolysis to give the corresponding compoundof formula I in which R¹ is hydrogen. Suitable acyl groups include:alkanoyl, for example C₂ to C₆ alkanoyl; aroyl, for example benzoyl andsubstituted benzoyl wherein the benzene ring is substituted with fromone to three substituents chosen from the group consisting of halogen,nitro, cyano, C₁ to C₆ alkyl, C₁ to C₆ haloalkyl, C₁ to C₆ alkoxy and C₁to C₆ alkylthio; and heteroaroyl, for example 2-furoyl, 3-furoyl,2-thenoyl and 3-thenoyl.

When in the compound of formula I R¹ is chosen from an inorganic ororganic cation the nature of the cations is not narrowly critical.Although not intending to be bound by theory, it is believed that whenR¹ is a cation the cation may be removed in the plant to give a compoundof formula I wherein R¹ is hydrogen. Suitable inorganic cations includethe alkali and alkaline earth metal ions, heavy metal ions including thetransition metal ions, and the ammonium ion. Suitable organic cationsinclude the cation R⁴ R⁵ R⁶ R⁷ N.sup.⊕ wherein R⁴, R⁵, R⁶ and R⁷ areindependently chosen from the group consisting of: hydrogen; C₁ to C₁₀alkyl; substituted C₁ to C₁₀ alkyl wherein the alkyl group issubstituted with a substituent chosen from the group consisting ofhydroxy, halogen and C₁ to C₆ alkoxy; phenyl; benzyl; and the groupssubstituted phenyl and substituted benzyl wherein the benzene ring issubstituted with from one to three substituents chosen from the groupconsisting of halogen, nitro, cyano, C₁ to C₆ alkyl, C₁ to C₆ haloalkyl,C₁ to C₆ alkoxy and C₁ to C₆ alkylthio.

It should be recognized that when R¹ is hydrogen the compounds of theinvention may exist in any one of three tautomeric forms as shown below.##STR3##

Suitable X include halogen, nitro, cyano, C₁ to C₆ alkyl and C₁ to C₆alkoxy.

Suitable R¹ include hydrogen, benzoyl, substituted benzoyl wherein thebenzene ring is substituted with from one to three substituents chosenfrom the group consisting of halogen, nitro, C₁ to C₆ alkyl, C₁ to C₆alkoxy and C₁ to C₆ haloalkyl, and the group M wherein M is an alkalimetal ion.

Suitable R² include C₁ to C₆ alkyl, C₂ to C₆ alkenyl, C₂ to C₆ alkynyl,benzyl and substituted benzyl wherein the benzene ring is substitutedwith from one to three substituents chosen from the group consisting ofhalogen, nitro, C₁ to C₆ alkyl, C₁ to C₆ alkoxy and C₁ to C₆ haloalkoxy.

Suitable R³ include C₁ to C₆ alkyl.

Suitable n include zero or an integer chosen from 1 to 3.

Suitable m include zero or an integer chosen from 1 and 2.

Preferred W include C₁ to C₃ alkyl.

Preferred X include: halogen; nitro; cyano; hydroxy; C₁ to C₄ alkyl; C₁to C₄ alkoxy; C₂ to C₄ alkenyloxy; C₁ to C₄ alkylthio; C₁ to C₄alkylsulfinyl; C₁ to C₄ alkylsulfonyl; formyl, C₂ to C₆ alkanoyl and theoxime O-C₁ to C₄ alkyl ethers thereof; C₂ to C₆ alkanoyloxy; benzyloxy;sulfamoyl; N,N-di(C₁ to C₄ alkyl)sulfamoyl; C₁ to C₄ alkyl substitutedwith a substituent selected from the group consisting of nitro, hydroxy,C₁ to C₄ alkoxy and C₁ to C₄ alkylthio; C₁ to C₄ alkoxy substituted withone or more substituents selected from halogen; the group NR⁸ R⁹ whereinR⁸ and R⁹ are independently selected from hydrogen and C₂ to C₄alkanoyl; and the group --(CH₂)_(q) -- which bridges two adjacent carbonatoms of the benzene ring and wherein q is an integer selected from 3and 4.

Preferred R¹ include: hydrogen; C₂ to C₆ alkanoyl such as acetyl;benzoyl and substituted benzoyl wherein the benzene ring is substitutedwith from one to three substituents selected from the group consistingof halogen, nitro, C₁ to C₆ alkyl and C₁ to C₆ alkoxy; benzenesulfonyland substituted benzenesulfonyl wherein the benzene ring is substitutedwith from one to three substitutents selected from the group consistingof halogen, nitro, C₁ to C₆ alkyl and C₁ to C₆ alkoxy; and an inorganicor organic cation selected from the cations of the alkali metals such aslithium, potassium and sodium, the cations of the alkaline earth metalssuch as magnesium, calcium and barium, the cations of the transitionmetals such as manganese, copper, zinc, iron, nickel, cobalt and silver,the ammonium ion and the triand tetra-(alkyl) ammonium ions whereinalkyl is selected from C₁ to C₆ alkyl and C₁ to C₆ hydroxyalkyl.

Preferred R² include: C₁ to C₆ alkyl; C₂ to C₆ alkenyl; C₂ to C₆alkynyl; C₁ to C₆ haloalkyl; C₂ to C₆ haloalkenyl; and C₂ to C₆haloalkynyl.

Preferred R³ include C₁ to C₆ alkyl.

Preferred n is an integer chosen from 1 and 2.

More preferred compounds of the invention include those compounds offormula I in which n is 1. That is compounds of formula ##STR4##wherein: W is methyl;

X is selected from the group consisting of halogen, C₁ to C₄ alkyl, C₁to C₄ alkoxy, C₁ to C₄ alkylthio, sulfamoyl, N,N-di(C₁ to C₄alkyl)sulfamoyl, and the group --(CH₂)₃ -- which bridges two adjacentcarbon atoms of the benzene ring;

R¹ is selected from the group consisting of hydrogen, acetyl, benzoyl,substituted benzoyl wherein the benzene ring is substituted with asubstituent chosen from nitro, halogen, methyl and methoxy,benzenesulfonyl, substituted benzenesulfonyl wherein the benzene ring issubstituted with a substituent chosen from nitro, halogen, methyl andmethoxy, the cations of the alkali metals, the cations of the transitionmetals, the ammonium ion and the tri- and tetra-(alkyl) ammonium ionswherein alkyl is selected from C₁ to C₆ alkyl and C₁ to C₆ hydroxyalkyl;

R² is selected from the group consisting of C₁ to C₃ alkyl, C₁ to C₃haloalkyl, allyl and haloallyl;

R³ is selected from C₁ to C₃ alkyl;

p is zero or an integer chosen from 1 to 3; and

m is zero or an integer chosen from 1 to 3.

Included among the more preferred compounds of the invention are those4-indanyl compounds which are further substituted in the 7-position ofthe indane ring. That is, compounds of formula ##STR5## wherein: W ismethyl;

X and X⁷ are independently selected from the group consisting of methyl,methoxy and halogen;

R¹ is selected from the group consisting of hydrogen, acetyl, benzoyl,nitrobenzoyl, methylbenzenesulfonyl and the cations of the alkalimetals;

R² is selected from the group consisting of C₁ to C₃ alkyl, 2-haloethyl,allyl and 2-haloallyl;

R³ is selected from C₁ to C₃ alkyl;

p is zero or an integer chosen from 1 and 2; and

m is zero or an integer chosen from 1 and 2.

Also included among the more preferred compounds of the invention arethose 5-indanyl compounds which are further substituted in at least oneof the 4- and 6-positions of the indane ring. That is, compounds offormula ##STR6## wherein: W is methyl;

X⁴ and X⁶ are independently selected from the group consisting ofhydrogen, methyl, methoxy and halogen and at least one of X⁴ and X⁶ isnot hydrogen;

X⁷ is selected from the group consisting of hydrogen, methyl, methoxy,halogen and N,N-di(methyl)sulfamoyl;

R¹ is selected from the group consisting of hydrogen, acetyl, benzoyl,nitrobenzoyl, methylbenzenesulfonyl and the cations of the alkalimetals;

R² is selected from the group consisting of C₁ to C₃ alkyl, 2-haloethyl,allyl and 2-haloallyl;

R³ is selected from C₁ to C₃ alkyl; and

p is zero or an integer chosen from 1 and 2.

Included among the even more preferred compounds of the invention arethose 4-indanyl compounds which are further substituted in the 5- and7-positions of the indane ring. That is, compounds of formula ##STR7##wherein: X⁵ is selected from the group consisting of methyl, methoxy andhalogen;

X⁶ is selected from the group consisting of hydrogen, methyl, methoxyand halogen;

X⁷ is methyl;

R¹ is selected from the group consisting of hydrogen, acetyl, sodium andpotassium;

R² is selected from ethyl and allyl; and

R³ is selected from ethyl and n-propyl.

Also included among the even more preferred compounds of the inventionare those 5-indanyl compounds which are further substituted in the 4-and 6-positions of the indane ring. That is compounds of formula##STR8## wherein: X⁴ and X⁶ are independently selected from the groupconsisting of methyl, methoxy and halogen;

X⁷ is selected from the group consisting of hydrogen, methyl, methoxyand halogen;

R¹ is selected from the group consisting of hydrogen, acetyl, sodium andpotassium;

R² is selected from ethyl and allyl; and

R³ is selected from ethyl and n-propyl.

Specific examples of the compounds of the invention include thosecompounds detailed in Tables 1a to 1e.

                  TABLE 1a                                                        ______________________________________                                         ##STR9##                                                                     Compound                                                                      No      (X).sub.m + (W).sub.p                                                                      R.sup.1 R.sup.2   R.sup.3                                ______________________________________                                        1       H            H       C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                        2       H            Na.sup.+                                                                              C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                        3       H            a       C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                        4       H            H       CH.sub.2 CHCH.sub.2                                                                     C.sub.2 H.sub.5                        5       H            H       C.sub.2 H.sub.5                                                                         n-C.sub.3 H.sub.7                      6       H            H       CH.sub.2 CHCH.sub.2                                                                     n-C.sub.3 H.sub.7                      8       4,7-(CH.sub.3).sub.2                                                                       H       C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                        9       4,6-(CH.sub.3).sub.2                                                                       H       C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                        11      4,6,7-(CH.sub.3).sub.3                                                                     H       C.sub. 2 H.sub.5                                                                        C.sub.2 H.sub.5                        13      7-Br-4,6-(CH.sub.3).sub.2                                                                  H       C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                        14      2,2,4,7-(CH.sub.3).sub.4                                                                   H       C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                        15      2,2,4,6,7-(CH.sub.3).sub.5                                                                 H       C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                        16      2,2-(CH.sub.3).sub.2                                                                       H       C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                        17      4,6-(CH.sub.3).sub.2 -7-                                                                   H       C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                SO.sub.2 N(CH.sub.3).sub.2                                            18      4,7-(CH.sub.3).sub.2 -6-                                                                   H       C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                SO.sub.2 N(CH.sub.3).sub.2                                            19      6-Br-4,7-(CH.sub.3).sub.2                                                                  H       C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                        20      4,7-(CH.sub.3).sub.2 -6-C.sub.2 H.sub.5                                                    H       C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                        21      7-Cl-4,6-(CH.sub.3).sub.2                                                                  H       C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                        22      4-Cl-6,7-(CH.sub.3).sub.2                                                                  H       C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                        23      6-Br-4,7-(CH.sub.3).sub.2                                                                  H       C.sub.2 H.sub.5                                                                         n-C.sub.3 H.sub.7                      24      6-Cl-4,7-(CH.sub.3).sub.2                                                                  H       C.sub.2 H.sub.5                                                                         n-C.sub.3 H.sub.7                      25      6-Cl-4,7-(CH.sub.3).sub.2                                                                  H       C.sub.2 H.sub.5                                                                         C.sub.6 H.sub.5                        46      2-CH.sub.3   H       C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                        47      1,1,4,6,7-(CH.sub.3).sub.5                                                                 H       C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                        48      1,1,2,4,6,7-(CH.sub.3).sub.6                                                               H       C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                        49      1,1,2,4,6,7-(CH.sub.3).sub.6                                                               H       C.sub.2 H.sub.5                                                                         n-C.sub.3 H.sub.7                      50      3,4,6,7-(CH.sub.3).sub.4                                                                   H       C.sub.2 H.sub.5                                                                         n-C.sub.3 H.sub.7                      51      2,4,6,7-(CH.sub.3).sub.4                                                                   H       C.sub.2 H.sub.5                                                                         n-C.sub.3 H.sub.7                      ______________________________________                                         Footnote to Table 1a                                                          a C.sub.6 H.sub.5 CO                                                     

                  TABLE 1b                                                        ______________________________________                                         ##STR10##                                                                    Com-                                                                          pound                                                                         No    (X).sub.m + (W).sub.p                                                                         R.sup.1  R.sup.2 R.sup.3                                ______________________________________                                        10    5,7-(CH.sub.3).sub.2                                                                          H        C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                        12    5,6,7-(CH.sub.3).sub.3                                                                        H        C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                        26    6-Cl-5,7-(CH.sub.3).sub.2                                                                     H        C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                        31    5,6,7-(CH.sub.3).sub.3                                                                        Na.sup.+ C.sub.2 H.sub.5                                                                       n-C.sub.3 H.sub.7                      32    5,6,7-(CH.sub.3).sub.3                                                                        a        C.sub.2 H.sub.5                                                                       n-C.sub.3 H.sub.7                      33    5-Br-6,7-(CH.sub.3).sub.2                                                                     Na.sup.+ C.sub.2 H.sub.5                                                                       n-C.sub.3 H.sub.7                      34    6-F-5,7-(CH.sub.3).sub.2                                                                      H        C.sub.2 H.sub.5                                                                       n-C.sub.3 H.sub.7                      35    6-F-5,7-(CH.sub.3).sub.2                                                                      Na.sup.+ C.sub.2 H.sub.5                                                                       n-C.sub.3 H.sub.7                      36    5,6,7-(CH.sub.3).sub.3                                                                        Li.sup.+ C.sub.2 H.sub.5                                                                       n-C.sub.3 H.sub.7                      37    5,6,7-(CH.sub.3).sub.3                                                                        CH.sub.3 CO                                                                            C.sub.2 H.sub.5                                                                       n-C.sub.3 H.sub.7                      38    5,6,7-(CH.sub.3).sub.3                                                                        b        C.sub.2 H.sub.5                                                                       n-C.sub.3 H.sub.7                      39    5,6,7-(CH.sub.3).sub.3                                                                        H        c       n-C.sub.3 H.sub.7                      40    5,6,7-(CH.sub.3).sub.3                                                                        1/2Cu.sup. ○2+                                                                  C.sub.2 H.sub.5                                                                       n-C.sub.3 H.sub.7                      41    5,6,7-(CH.sub.3).sub.3                                                                        1/2Ni.sup. ○2+                                                                  C.sub.2 H.sub.5                                                                       n-C.sub.3 H.sub.7                      42    5,6,7-(CH.sub.3).sub.3                                                                        d        C.sub.2 H.sub.5                                                                       n-C.sub.3 H.sub.7                      43    5,6,7-(CH.sub.3).sub.3                                                                        e        C.sub.2 H.sub.5                                                                       n-C.sub.3 H.sub.7                      44    5,6,7-(CH.sub.3).sub.3                                                                        H        CH.sub.2 CH.sub.2 F                                                                   n-C.sub.3 H.sub.7                      45    5,6,7-(CH.sub.3).sub.3                                                                        H        C.sub.2 H.sub.5                                                                       C.sub.6 H.sub.5                        52    2,2,5,6,7-(CH.sub.3).sub.5                                                                    H        C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                        53    2,2,5,6,7-(CH.sub.3).sub.5                                                                    H        C.sub.2 H.sub.5                                                                       n-C.sub.3 H.sub.7                      54    3,3,5,6,7-(CH.sub.3 ).sub.5                                                                   H        C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                        55    2,5,6,7-(CH.sub.3).sub.4                                                                      H        C.sub.2 H.sub.5                                                                       n-C.sub.3 H.sub.7                      56    1,5,6,7-(CH.sub.3).sub.4                                                                      H        C.sub.2 H.sub.5                                                                       n-C.sub.3 H.sub.7                      57    5-CH.sub.2 CH.sub.2 CH.sub.2 -6                                                               H        C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                        58    5-CH.sub.2 CH.sub.2 CH.sub.2 -6                                                               H        C.sub.2 H.sub.5                                                                       n-C.sub.3 H.sub.7                      59    7-CH.sub.3 -5-CH.sub.2 CH.sub.2 CH.sub.2 -6                                                   H        C.sub.2 H.sub.5                                                                       n-C.sub.3 H.sub.7                      60    5-Br-6,7-(CH.sub.3).sub.2                                                                     H        C.sub.2 H.sub.5                                                                       n-C.sub.3 H.sub.7                      61    5,6,7-(CH.sub.3).sub.3                                                                        H        C.sub.2 H.sub.5                                                                       n-C.sub.3 H.sub.7                      ______________________________________                                         Footnotes to Table 1b                                                         a C.sub.6 H.sub.5 CO                                                          b 4CH.sub.3 C.sub.6 H.sub.4 SO.sub.2                                          c CH.sub.2 CBrCH.sub.2                                                        d 4NO.sub.2 C.sub.6 H.sub.4 CO                                                e N(nC.sub.4 H.sub.9).sub.4                                              

                  TABLE 1c                                                        ______________________________________                                         ##STR11##                                                                    Compound                                                                      No        (X).sub.m + (W).sub.p                                                                        R.sup.1                                                                             R.sup.2                                                                              R.sup.3                                 ______________________________________                                        27        2,3,4-(CH.sub.3).sub.3                                                                       H     C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                         28        2,3,4-(CH.sub.3).sub.3                                                                       H     C.sub.2 H.sub.5                                                                      n-C.sub.3 H.sub.7                       30        3,4-(CH.sub.3).sub.2 -2-OCH.sub.3                                                            H     C.sub.2 H.sub.5                                                                      n-C.sub.3 H.sub.7                       ______________________________________                                    

                  TABLE 1d                                                        ______________________________________                                         ##STR12##                                                                    Compound                                                                      No          (X).sub.m + (W).sub.p                                                                    R.sup.1  R.sup.2                                                                            R.sup.3                                  ______________________________________                                        7           H          H        C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                          ______________________________________                                    

                  TABLE 1e                                                        ______________________________________                                         ##STR13##                                                                    Compound                                                                      No         (X).sub.m + (W).sub.p                                                                    R.sup.1  R.sup.2                                                                            R.sup.3                                   ______________________________________                                        29         2,3,4-(CH.sub.3).sub.3                                                                   H        C.sub.2 H.sub.5                                                                    n-C.sub.3 H.sub.7                         ______________________________________                                    

The compounds of the invention may be prepared by a variety of methodsand in a further aspect the invention provides methods for thepreparation of compounds of formula I.

Conveniently the preparation of the compounds of the invention can beconsidered in three or four parts.

Part A involves the formation of a 5-(substitutedaryl)cyclohexane-1,3-dione of formula IX. This reaction may be carriedout in a two step process by condensing an aldehyde derivative offormula V with acetone to form a ketone of formula VI, which is in turncondensed with a malonic acid ester of formula VII to give a5-(substituted aryl)cyclohexane-1,3-dione of formula IX, either with orwithout the isolation of the intermediate of formula VIII.

Alternatively, this preparation may be carried out in a two step processby condensing an aldehyde derivative of formula V with a malonic acidester of formula VII to give an arylmethylidenemalonate derivative offormula X which is in turn condensed with an acetoacetic acid ester offormula XI to give a 5-(substituted aryl)cyclohexane-1,3-dione offormula IX, either with or without isolation of the intermediate offormula XII.

In a further alternative process this preparation may be carried out bycondensing a 2-arylalkenoate derivative of formula XXI with anacetoacetic acid ester of formula XI to give a 5-(substitutedaryl)cyclohexan-1,3-dione of formula IX, either with or withoutisolation of the intermediate of formula VIII.

The above reaction sequences are set out in SCHEME A parts (i), (ii) and(iii) respectively below, wherein R represents a C₁ to C₆ alkyl group.##STR14##

Part B involves the acylation of a compound of formula IX to give a2-acyl-5-(substituted aryl)cyclohexane-1,3-dione of formula XIII. Thisreaction may be carried out by reacting a 5-(substitutedaryl)cyclohexane-1,3-dione of formula IX with:

(iv) a mixture of an acid anhydride of formula XIV and either a salt ofthat acid or an alkoxide salt wherein M is an alkali metal ion and R isC₁ to C₆ alkyl;

(v) a mixture of an acid anhydride of formula XIV and the correspondingacid;

(vi) an acid halide of formula XV;

(vii) a mixture of an acid halide of formula XV and the correspondingacid; or

(viii) an alkali metal or alkaline earth metal hydride followed byreaction with an acid anhydride of formula XIV or an acid chloride offormula XV.

Alternatively this reaction may be carried out by:

(ix) reacting a 5-(substituted aryl)cyclohexane-1,3-dione of formula IXwith an acid halide of formula XV in the presence of pyridine to give anintermediate O-acyl derivative of formula XVI; and

(x) reacting the intermediate of formula XVI with a Lewis acid catalyst;

(xi) reacting the intermediate of formula XVI with the correspondingacid of the acid halide of formula XV; or

(xii) reacting the intermediate of formula XVI with imidazole.

Each of these reactions is outlined in SCHEME B below wherein halrepresents halogen. ##STR15##

Part C involves the formation of a compound of the invention of formulaI wherein R¹ is hydrogen, that is a compound of formula II. Thisreaction may be carried out either:

(xiii) by reacting a compound of formula XIII with an alkoxyaminederivative of formula XVII to give a compound of formula II; or

(xiv) by reacting a compound of formula XIII with hydroxylamine to givean intermediate oxime derivative of formula XVIII and reacting the oximederivative of formula XVIII with an alkylating agent of formula XIX togive a compound of formula II.

These reaction sequences are set out in SCHEME C below wherein L is agood leaving group such as, for example, chloride, bromide, iodide,sulfate, nitrate, methyl sulfate, ethyl sulfate, tetrafluoroborate,hexafluorophosphate, hexafluoroantimonate, methanesulfonate,fluorosulfonate, fluoromethanesulfonate and trifluoromethanesulfonate.##STR16##

Compounds of the invention of formula I wherein R¹ is not hydrogen maybe prepared from compounds of the invention of formula I wherein R¹ ishydrogen, that is, compounds of formula II, by etherification, acylationor sulfonylation as required. This reaction is outlined in SCHEME Dbelow. ##STR17##

Compounds of the invention of formula I wherein R¹ is an inorganic ororganic cation may be prepared from the compounds of the invention offormula I wherein R¹ is hydrogen, that is, compounds of formula II, byreacting said compounds of formula II with an inorganic or organic salt.For example, the compounds of formula I wherein R¹ is an alkali metalion may be prepared by reacting the appropriate compound of formula IIwith the appropriate alkali metal hydroxide or alkoxylate. The compoundsof formula I wherein R¹ is a transition metalion or an organic cationmay similarly be prepared by reacting the appropriate compound offormula II with an appropriate transition metal salt or organic base.Alternatively, the compounds of formula I wherein R¹ is a transitionmetal ion or an organic cation may be prepared by reacting theappropriate compound of formula I wherein R¹ is an alkali metal ion withan appropriate transition metal salt or organic salt.

Accordingly, in a further aspect the invention provides a process forthe preparation of a compound of formula I, wherein W, X, R¹, R², R³, p,m and n are as hereinbefore defined, which process comprises:

a) reacting an aldehyde derivative of formula V with acetone to give aketone derivative of formula VI and reacting the ketone derivative offormula VI with a malonic acid ester of formula VII, wherein R is C₁ toC₆ alkyl, to give a 5-(substituted aryl)cyclohexane-1,3-dione derivativeof formula IX; or reacting an aldehyde derivative of formula V with amalonic acid ester of formula VII to give an arylmethylidenemalonatederivative of formula X and reacting the arylmethylidenemalonatederivative of formula X with an acetoacetic acid ester fo formula XI,wherein R is C₁ to C₆ alkyl, to give a 5-(substitutedaryl)cyclohexane-1,3-dione derivative of formula IX; or reacting a2-arylalkenoate derivative of formula XXI, wherein R is C₁ to C₆ alkyl,with an acetoacetic acid ester of formula XI, wherein R is C₁ to C₆alkyl, to give a 5-(substituted phenyl)cyclohexane-1,3-dione derivativeof formula IX;

b) acylating the 5-(substituted aryl)cyclohexane-1,3-dione derivative offormula IX with an acid anhydride of formula XIV or an acid halide offormula XV to give a 2-acyl-5-(substituted aryl)cyclohexane-1,3-dionederivative of formula XIII;

c) reacting the 2-acyl-5-(substituted aryl)-cyclohexane-1,3-dionederivative of formula XIII with an alkoxyamine derivative of formulaXVII to give a compound of the invention of formula II or reacting the2-acyl-5-(substituted aryl) cyclohexane-1,3-dione derivative of formulaXIII with hydroxylamine and alkylating the oxime intermediate of formulaXVIII with an alkylating agent of formula XIX, wherein L is a goodleaving group, to give a compound of the invention of formula II; andoptionally

d) reacting the compound of the invention of formula II with a compoundof formula XX, wherein L is a good leaving group, to give a compound ofthe invention of formula I.

Certain of the intermediate compounds of formula VI, VIII, IX, X, XII,XXI, XIII, XVI and XVIII are novel compounds are therefore as a furtherembodiment the invention provides novel compounds of formulae VI, VIII,IX, X, XII, XXI, XIII, XVI and XVIII, wherein the substituents are ashereinbefore defined, and processes for the preparation thereof.

The compounds of formula I are active as herbicides and therefore, in afurther aspect the invention provides a process for severely damaging orkilling unwanted plants which process comprises applying to the plants,or to the growth medium of the plants, an effective amount of a compoundof formula I as hereinbefore defined.

The compounds of formula I are active as herbicides againstmonocotyledonous weeds, wild grasses, and in particular are selectivelyactive against difficulty controllable wild grasses in crops ofcultivated plants. The compounds of the invention are especially usefulin the control of wild grasses such as wild oats and rye grass in cropsof cultivated monocotyledonous plants such as wheat, barley and othervarieties of cereals.

Accordingly, in yet a further aspect the invention provides a processfor controlling monocotyldonous weeds in cultivated crops, especiallywild grasses in cereal crops such as wheat and barley, which processcomprises applying to the crop, or to the growth medium of the crop, acompound of formula I, as hereinbefore defined, in an amount sufficientto severely damage or kill the weeds but insufficient to damage the cropsubstantially.

The compounds of formula I may be applied directly to the plant(post-emergence application) or to the soil before the emergence of theplant (pre-emergence application). However, the compounds are, ingeneral, more effective when applied to the plant post-emergence.

The compounds of formula I may be used on their own to inhibit thegrowth of, severely damage, or kill plants but are preferably used inthe form of a composition comprising a compound of the invention inadmixture with a carrier comprising a solid or liquid diluent.Therefore, in yet a further aspect the invention provides plant growthinhibiting, plant damaging, or plant killing compositions comprising acompound of formula I as hereinbefore defined and an inert carriertherefor.

Certain of the compounds of formula I exhibit useful plant growthregulating activity. For example, while compounds of formula I areselectively active herbicides against wild grasses in crops ofcultivated plants at some rates of application they exhibit plant growthregulating effects in said crops.

Plant growth regulating effects may be manifested in a number of ways.For example, suppression of apical dominance, stimulation of auxiliarybud growth, stimulation of early flowering and seed formation,enhancement of flowering and increase in seed yield, stem thickening,stem shortening and tillering. Plant growth regulating effects shown bycompounds of the invention include, for example tillering and stemshortening in crops such as wheat and barley.

Accordingly in a still further aspect the invention provides a processfor regulating the growth of a plant which process comprises applying tothe plant, to the seed of the plant, or to the growth medium of theplant, an effective amount of a compound of formula I, as hereinbeforedefined.

To effect the plant growth regulating process of the present inventionthe compounds of formula I may be applied directly to the plant(post-emergence application) or to the seed or soil before the emergenceof the plant (post-emergence) application.

The compounds of formula I may be used on their own to regulate thegrowth of plants but in general are preferably used in the form of acomposition comprising a compound of the invention in admixture with acarrier comprising a solid or liquid diluent. Therefore, in a stillfurther aspect the invention provides plant growth regulatingcompositions comprising a compound of formula I as hereinbefore definedand an inert carrier therefor.

The compositions of the present invention may be in the form of solids,liquids or pastes. The compositions include both dilute compositionswhich are ready for immediate use and concentrated compositions whichmay require dilution before use. Therefore, the concentration of theactive ingredient in the compositions of the present invention will varydepending on the types of formulation and whether the composition isready for use such as, for example, a dust formulation or an aqueousemulsion or whether the composition is a concentrate such as, forexample, an emulsifiable concentrate or a wettable powder, which issuitable for dilution before use. In general the compositions of thepresent invention comprise from 1 ppm to 99% by weight of activeingredient.

The solid compositions may be in the form of powders, dusts, pellets,grains, and granules wherein the active ingredient is mixed with a soliddiluent. Powders and dusts may be prepared by mixing or grinding theactive ingredient with a solid carrier to give a finely dividedcomposition. Granules, grains and pellets may be prepared by bonding theactive ingredient to a solid carrier, for example, by coating orimpregnating the preformed granular solid carrier with the activeingredient or by agglomeration techniques.

Examples of solid carriers include: mineral earths and clays such as,for example, kaolin, bentonite, kieselguhr, Fuller's earth, Attaclay,diatomaceous earth, bole, loess, talc, chalk, dolomite, limestone, lime,calcium carbonate, powdered magnesia, magnesium oxide, magnesiumsulfate, gypsum, calcium sulfate, pyrophyllite, silicic acid, silicatesand silica gels; fertilizers such as, for example, ammonium sulfate,ammonium phosphate, ammonium nitrate and urea; natural products ofvegetable origin such as, for example, grain meals and flours, barkmeals, wood meals, nutshell meals and cellulosic powders; and syntheticpolymeric materials such as, for example, ground or powdered plasticsand resins.

Alternatively, the solid compositions may be in the form of dispersibleor wettable dusts, powders, granules or grains wherein the activeingredient and the solid carrier are combined with one or more surfaceactive agents which act as wetting, emulsifying and/or dispersing agentsto facilitate the dispersion of the active ingredient in liquid.

Examples of surface active agents include those of the cationic, anionicand non-ionic type. Cationic surface active agents include quaternaryammonium compounds, for example, the long chain alkylammonium salts suchas cetyltrimethylammonium bromide. Anionic surface active agentsinclude: soaps or the alkali metal, alkaline earth metal and ammoniumsalts of fatty acids; the alkali metal, alkaline earth metal andammonium salts of ligninsulfonic acid; the alkali metal, alkaline earthmetal and ammonium salts of arylsulfonic acids including the salts ofnaphthalenesulfonic acids such as butylnaphththalenesulfonic acid, thedi- and tri- isopropylnaphthalenesulfonic acids, the salts of thecondensation products of sulfonated naphthalene and naphthalenederivatives with formaldehyde, the salts of the condensation products ofsulfonated naphthalene and napththalene derivatives with phenol andformaldehyde, and the salts of alkylarylbenzenesulfonic acids such asdodecylbenzenesulfonic acid; the alkali metal, alkaline earth metal andammonium salts of the long chain mono esters of sulfuric acid oralkylsulfates such as laurylsulfate and the mono esters of sulfuric acidwith fatty alcohol glycol ethers. Nonionic surface active agentsinclude: the condensation products of ethylene oxide with fatty alcoholssuch as oleyl alcohol and cetyl alcohol; the condensation products ofethylene oxide with phenols and alkylphenols such as isooctylphenol,octylphenol and nonylphenol; the condensation products of ethylene oxidewith castor oil; the partial esters derived from long chain fatty acidsand hexitol anhydrides, for example sorbitan monolaurate, and theircondensation products with ethylene oxide; ethylene oxide/propyleneoxide block copolymers; lauryl alcohol polyglycol ether acetal; and thelecithins.

The liquid compositions may comprise a solution or dispersion of theactive ingredient in a liquid carrier optionally containing one or moresurface active agents which act as wetting, emulsifying and/ordispersing agents. Examples of liquid carriers include: water; mineraloil fractions such as, for example, kerosene, solvent naphtha,pertroleum, coal tar oils and aromatic petroleum fractions; aliphatic,cycloaliphatic and aromatic hydrocarbons such as, for example, paraffin,cyclohexane, toluene, the xylenes, tetrahydronaphthalene and alkylatednaphthalenes; alcohols such as, for example, methanol, ethanol,propanol, isopropanol, butanol, cyclohexanol and propylene glycol;ketones such as, for example, cyclohexanone and isophorone; and stronglypolar organic solvents such as, for example, dimethylformamide,dimethylsulfoxide, N-methylpyrrolidone and sulfolane.

A preferred liquid composition comprises an aqueous suspension,dispersion or emulsion of the active ingredient which is suitable forapplication by spraying, atomizing or watering. Such aqueouscompositions are generally prepared by mixing concentrated compositionswith water. Suitable concentrated compositions include emulsionconcentrates, pastes, oil dispersions, aqueous suspensions and wettablepowders. The concentrates are usually required to withstand storage forprolonged periods and after such storage to be capable of dilution withwater to form aqueous preparations which remain homogeneous for asufficient time to enable them to be applied by conventional sprayequipment. The concentrates conveniently contain from 20 to 99%,preferably 20 to 60%, by weight of active ingredient.

Emulsion or emulsifiable concentrates are conveniently prepared bydissolving the active ingredient in an organic solvent containing one ormore surface active agents. Pastes may be prepared by blending thefinely divided active ingredient with a finely divided solid carrier,one or more surface active agents and optionally an oil. Oil dispersionsmay be prepared by grinding together the active ingredient, ahydrocarbon oil, and one or more surface active agents. Aqueoussuspension concentrates may conveniently be prepared by ball milling amixture of the active ingredient, water, at least one surface activeagent and preferably at least one suspending agent. Suitable suspendingagents include: hydrophilic colloids such as, for example,poly-(N-vinylpyrrolidone), sodium carboxymethylcellulose and thevegetable gums gum acacia and gum tragacanth; hydrated colloidal mineralsilicates such as, for example, montmorillonite, beidellite, nontronite,hectorite, saponite, sauconite and bentonite; other cellulosederivatives; and poly(vinyl alcohol). Wettable powder concentrates mayconveniently be prepared by blending together the active ingredient, oneor more surface active agents, one or more solid carriers and optionallyone or more suspending agents and grinding the mixture to give a powderhaving the required particle size.

The aqueous suspensions, dispersions or emulsions may be prepared fromthe concentrated compositions by mixing the concentrated compositionswith water optionally containing surface active agents and/or oils.

It should be noted that the compounds of the invention of formula Iwherein R¹ is hydrogen are acidic. Therefore, the compounds of formula Imay be formulated and applied as the salts of organic or inorganicbases. In formulating and employing the compounds of formula I in theform of their salts either the salts per se, that is the compounds offormula I wherein R¹ is an inorganic or an organic cation, may be usedin the formulation or the compounds of formula I wherein R¹ is hydrogenmay be used in the formulation and the salts generated in situ by theuse of the appropriate organic or inorganic base.

The mode of application of the compositions of the invention will dependto a large extent on the type of composition used and the facilitiesavailable for its application. Solid compositions may be applied bydusting or any other suitable means for broadcasting or spreading thesolid. Liquid compositions may be applied by spraying, atomizing,watering, introduction into the irrigation water, or any other suitablemeans for broadcasting or spreading the liquid.

The rate of application of the compounds of the invention will depend ona number of factors including, for example, the compound chosen for use,the identity of the plants whose growth is to be inhibited theformulations selected for use and whether the compound is to be appliedfor foliage or root uptake. As a general guide, however, an applicationrate of from 0.005 to 20 kilograms per hectare is suitable while from0.01 to 5.0 kilograms per hectare may be preferred.

The compositions of the invention may comprise, in addition to one ormore compounds of the invention, one or more compounds not of theinvention but which posses biological activity. For example, ashereinbefore indicated the compounds of the invention are in generalsubstantially more effective against monocotyledonous plants or grassspecies than against dicotyledonous plants or broad-leaved species. As aresult, in certain applications the herbicidal use of the compounds ofthe invention alone may not be sufficient to protect a crop. Accordinglyin yet a still further embodiment the invention provides a herbicidalcomposition comprising a mixture of at least one herbicidal compound offormula I as hereinbefore defined with at least one other herbicide.

The other herbicide may be any herbicide not having the formula I. Itwill generally be a herbicide having a complementary action. Forexample, one preferred class is of mixtures comprising a herbicideactive against broad-leaved weeds. A second preferred class is ofmixtures comprising a contact herbicide.

Example of useful complementary herbicides include:

A. benzo-2,1,3-thiadiazin-4-one-2,2-dioxides such as3-isopropylbenzo-2,1,3-thiadizin-4-one-2,2-dioxide (common namebentazon);

B. hormone herbicides and in particular the phenoxyalkanoic acids suchas 4-chloro-2-methylphenoxy acetic acid (common name MCPA),2-(2,4-dichlorophenoxy)propionic acid (common name dichlorprop),2,4,5-trichlorophenoxyacetic acid (common name 2,4,5-T),4-(4-chloro-2-methylphenoxy)butyric acid (common name MCPB),2,4-dichlorophenoxyacetic acid (common name 2,4-D),4-(2,4-dichlorophenoxy)butyric acid (common name 2,4-DB),2-(4-chloro-2-methylphenoxy)propionic acid (common name mecoprop), andtheir derivatives (eg salts, esters, amides and the like);

3-[4-(4-halophenoxy)phenyl]-1,1-dialkylureas such as3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea (common namechloroxuron);

D. dinitrophenols and their derivatives (eg acetates) such as2-methyl-4,6-dinitrophenol (common name DNOC),2-tertiarybutyl-4,6-dinitrophenol (common name dinoterb),2-secondarybutyl-4,6-dinitrophenol (common name dinoseb) and its esterdinoseb acetate;

E. dinitroaniline herbicides such asN',N'-diethyl-2,6-dinitro-4-trifluoromethyl-m-phenylenediamine (commonname dinitramine), 2,6-dinitro-N,N-dipropyl-4-trifluoromethylaniline(common name trifluralin) and4-methylsulfonyl-2,6-dinitro-N,N-dipropylaniline (common name nitralin);

F. phenylurea herbicides such asN'-(3,4-dichlorophenyl)-N,N-dimethylurea (common name diruon) andN,N-dimethyl-N'-[3-(trifluoromethyl)phenyl]urea (common namefluometuron);

G. phenylcarbamoyloxyphenylcarbamates such as3-[(methoxycarbonyl)amino]phenyl (3-methylphenyl)carbamate (common namephenmedipham) and 3-[(ethoxycarbonylamino]phenyl phenylcarbamate (commonname desmedipham);

H. 2-phenylpyridazin-3-ones such as5-amino-4-chloro-2-phenylpyridazin-3-one (common name pyrazon);

I. uracil herbicides such as 3-cyclohexyl-5,6-trimethyleneuracil (commonname lenacil), 5-bromo-3-sec-butyl-6-methyluracil (common name bromacil)and 3-tert-butyl-5-chloro-6-methyluracil (common name terbacil);

J. triazine herbicides such as2-chloro-4-ethylamino-6-(iso-propylamino)-1,3,5-triazine (common nameatrazine), 2-chloro-4,6-di(ethylamino)-1,3,5-triazine (common namesimazine) and 2-azido-4-(iso-propylamino)-6-methylthio-1,3,5-triazine(common name aziproptryne);

K. 1-alkoxy-2-alkyl-3-phenylurea herbicides such as3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea (common name linuron),3-(4-chlorophenyl)-1-methoxy-1-methylurea (common name monolinuron) and3-(4-bromo-4-chlorophenyl)-1-methoxy-1-methylurea (common namechlorobromuron);

L. thiolcarbamate herbicides such as S-propyl dipropylthiocarbamate(common name verolate);

M. 1,2,4-triazin-5-one herbicides such as4-amino-4,5-dihydro-3-methyl-6-phenyl-1,2,4,-triazine-5-one (common namemetamitron) and 4-amino-6-tert-butyl4,5-dihydro-3-methylthio-1,3,4-triazin-5-one (common name metribuzin);

N. benzoic acid herbicides such as 2,3,6-trichlorobenzoic acid (commonname 2,3,6-TBA), 3,6-dichloro-2-methoxybenzoic acid (common namedicamba) and 3-amino-2,5-dichlorobenzoic acid (common name chloramben).

O. anilide herbicides such asN-butoxymethyl-α-chloro-2',6'-diethylacetanilide (common namebutachlor), the corresponding N-methoxy compound (common name alachlor),the corresponding N-iso-propyl compound (common name propachlor) and3',4'-dichloropropionanilide (common name propanil);

P. dihalobenzonitrile herbicides such as 2,6-dichlorobenzonitrile(common name dichlobenil), 3,5-dibromo-4-hydroxybenzonitrile (commonname bromoxynil) and 3,5-diiodo-4-hydroxybenzonitrile (common nameioxynil).

Q. haloalkanoic herbicides such as 2,2-dichloropropionic acid (commonname dalapon), trichloroacetic acid (common name TCA) and salts thereof;

R. diphenylether herbicides such as 4-nitrophenyl2-nitro-4-trifluoromethylphenyl ether (common name fluorodifen), methyl5-(2,4-dichlorophenoxy)-2-nitrobenzoate (common name bifenox),2-nitro-5-(2-chloro-4-trifluoromethylphenoxy)benzoic acid and2-chloro-4-trifluoromethylphenyl 3-ethoxy-4-nitrophenyl ether;

S. N-(heteroarylaminocarbonyl)benzenesulfonamides such as2-chloro-N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]benzenesulfonamide(commonly known as DPX 4189); and

T. miscellaneous herbicides including N,N-dimethyldiphenylacetamide(common name diphenamid), N-(1-naphthyl)phthalamic acid (common namenaptalam) and 3-amino-1,2,4,-triazole.

Examples of useful contact herbicides include:

U. bipyridylium herbicides such as those in which the active entity isthe 1,1'-dimethyl-4,4'-dipyridylium ion (common name paraquat) and thosein which the active entity is the 1,1'-ethylene-2,2'-dipyridylium ion(common name diquat);

V. organoarsenical herbicides such as monosodium methanearsonate (commonname MSMA); and

W. amino acid herbicides such as N-(phosphonomethyl)glycine (common nameglyphosate) and its salts and esters.

The invention is now illustrated by, but in no way limited to, thefollowing examples.

EXAMPLE 1 4,7-Dimethylindane

(i) β-Chloropropionyl chloride (71.9 g, 566 mmole) was added to amixture of aluminium chloride (75.5 g, 566 mmole) and ethylenedichloride (200 ml). To this mixture was added p-xylene (60.0 g, 566mmole) and the solution was stirred at room temperature for 30 minutes,then poured into dilute hydrochloric acid. The organic layer wasseparated, washed with water and dried over anhydrous sodium sulfate.Evaporation of the solvent under reduced pressure gave2-(2-chloropropionyl)-2,4-dimethylbenzene a yellowish oil, which wasused immediately in the next step of the sequence.

(ii) The crude 2-(2-chloropropionyl)-1,4-dimethylbenzene was slowlyadded to concentrated sulfuric acid (400 ml), preheated to 105° C. Thesolution was then stirred at 105°-110° C. for 30 minutes. The cooledmixture was poured onto cracked ice and the precipitate collected togive 4,7-dimethylindan-1-one (59.4 g, 65.6%) as a pale solid, mp 70° C.

(iii) Zinc amalgam (prepared by mixing zinc dust (25.0 g), mercuricchloride (2.5 g), concentrated hydrochloric acid (3 ml) and water (50ml) together for 5 minutes, then decanting the aqueous solution) wasadded to a mixture of 4,7-dimethylindan-1-one (25.0 g, 156 mmole),acetic acid (50 ml), water (50 ml) and concentrated hydrochloric acid(100 ml). The mixture was refluxed with vigorous stirring for 12 hours,then cooled, poured into water and extracted with diethyl ether. Theether extract was washed successively with water, dilute aqueous sodiumbicarbonate solution and water. Then dried over anhydrous sodium sulfateand concentrated. Purification by column chromatography over silica gel(eluant hexane) gave 4,7-dimethylindane (18.5 g, 81.4%) as an oil.

The product was characterized by proton nuclear magnetic resonancespectroscopy and the spectroscopic data is recorded in Table 2.

EXAMPLE 2

The indane derivatives listed in Table 2 were prepared followingessentially the same procedure as that described in Example 1. Each ofthe products was characterized by proton nuclear magnetic resonancespectroscopy and spectroscopic data is recorded in Table 2 below.

                  TABLE 2                                                         ______________________________________                                        Indane Precursors to the Compounds of Formula I                               Indane                  Proton Chemical Shift                                 derivatives                                                                              Appearance   δ in ppm (CDCl.sub.3)                           ______________________________________                                        4,7-(CH.sub.3)                                                                           Colourless oil                                                                             1.90-2.20(8H, m); 2.80                                                        (4H, t); 6.80(2H, s).                                 5-Br-4,6-  Yellow oil   1.90-2.30(2H, m); 2.32                                (CH.sub.3).sub.2        (3H, s); 2.36(3H, s);                                                         2.81(4H, t); 6.94(1H, s)                              4,6,7-(CH.sub.3).sub.3                                                                   Colourless solid                                                                           1.90-2.23(11H, m); 2.80                                          mp <50° C.                                                                          (4H, m); 6.75(1H, s).                                 7-Br-4,6(CH.sub.3).sub.2                                                                 Colourless solid                                                                           1.90-2.20(5H, m); 2.30                                           mp <50° C.                                                                          (3H, s); 2.80-3.00                                                            (4H, m); 6.85(1H, s).                                 4,5,6-(CH.sub.3).sub.3                                                                   Colourless oil                                                                             1.90-2.25(11H, m);                                                            2.73-3.01(4H, m); 6.91                                                        (1H, s).                                              5-Br-4,7-(CH.sub.3).sub.2                                                                Colourless oil                                                                             1.90-2.20(5H, m); 2.27                                                        (3H, s); 3.30-4.00(4H, m);                                                    7.15(1H, s).                                          5-C.sub.2 H.sub.5 -4,7-                                                                  Colourless oil                                                                             1.15(3H, t); 1.90-2.20                                (CH.sub.3).sub.2        (8H, m); 2.60(2H, q);                                                         2.70-2.95(4H, m); 6.73                                                        (1H, s).                                              4-Cl-5,7-  Yellow oil   1.82-2.38(8H, m); 2.90                                (CH.sub.3).sub.2        (4H, m); 6.77(1H, s).                                 4-Cl-6,7-  Colourless oil                                                                             1.85-2.33(8H, m); 2.68-3.00                           (CH.sub.3).sub.2        (4H, m); 6.88(1H, s).                                 5-Cl-4,7-  White solid, mp                                                                            1.90-2.30(8H, m); 2.68-3.00                           (CH.sub.3).sub.2                                                                         <50° C.                                                                             (4H, m); 6.93(1H, s).                                 5-Cl-4,6-  Colourless oil                                                                             1.82-2.22(2H, m); 2.28                                (CH.sub.3).sub.2        (3H, s); 2.32(3H, s); 2.83                                                    (4H, t); 6.92(1H, s).                                 5-F-4,6-   Colourless oil                                                                             1.90-2.20(8H, m); 2.60-2.90                           (CH.sub.3).sub.2        (4H, m); 6.80(1H, d).                                 5-CH.sub.2 CH.sub.2 CH.sub.2 -6                                                          Colourless oil                                                                             2.05(4H, m); 2.85(8H, m);                                                     7.05(2H, s).                                          4-CH.sub.3 -5-CH.sub.2 -                                                                 Colourless oil                                                                             2.05(7H, m); 2.85(8H, m);                             CH.sub.2 CH.sub.2 -6    6.95(1H, s).                                          ______________________________________                                    

EXAMPLE 3 2,2,4,7-Tetramethylindane

4,7-Dimethylindan-1-one (6.00 g, 38 mmole) (see Example 1, parts (i) and(ii)) was dissolved in dimethylformamide (50 ml) and 60% sodium hydride(3.34 g; 76 mmole) was added portionwise over a period of 10 minutes.The mixture was allowed to stir for a further 10 minutes, then methyliodide (25 ml) was added portionwise and stirring continued at roomtemperature overnight. The mixture was poured onto cracked ice andextracted with diethyl ether. The ether extract was washed with water,dried over anhydrous sodium sulfate and evaporated under reducedpressure to give a dark oil. Treatment of the oil with zinc amalgam, asoutlined in Example 1, part (iii), gave a colourless oil, which waspurified by column chromatography over silica gel (eluant hexane) togive 2,2,4,7-tetramethylindane (5.35 g, 80.9%). The product wascharacterized by proton nuclear magnetic resonance spectroscopy and thespectroscopic data is recorded in Table 3.

EXAMPLE 4

The indane derivatives listed in Table 3 were prepared followingessentially the same procedure as that described in Example 3. Each ofthe products were characterized by proton nuclear magnetic resonancespectroscopy and the spectroscopic data is recorded in Table 3 below.

                  TABLE 3                                                         ______________________________________                                        Indane Precursors to the Compounds of Formula I                               Indane                  Proton Chemical Shift                                 derivatives                                                                              Appearance   δ in ppm (CDCl.sub.3)                           ______________________________________                                        2,2-(CH.sub.3).sub.2 -6-Br                                                               Colourless oil                                                                             1.14(6H, s); 2.65(4H, d);                                                     6.80-7.30(3H, m).                                     2,2,4,5,6-(CH.sub.3).sub.5                                                               Colourless oil                                                                             1.13(6H, s); 2.13(6H, s);                                                     2.22(3H, s); 2.62(4H, m);                                                     6.80(1H, s).                                          2,2,4,5,7-(CH.sub.3).sub.5                                                               Pale yellow oil                                                                            1.15(6H, s); 2.10(3H, s);                                                     2.15(3H, s); 2.23(3H, s);                                                     2.68(4H, m); 6.70(1H, s).                             2,2,4,7-(CH.sub.3).sub.4                                                                 Pale yellow oil                                                                            1.15(6H, s); 2.17(6H, s);                                                     2.65(4H, s); 6.84(1H, s).                             ______________________________________                                    

EXAMPLE 5

This example details the preparation of the indanes, which were preparedby methods directly analogous to those described in the literature.

METHOD A

The indanes were prepared following the general method described by T FWood and J Angiolini (Tetrahedron Letters, 1963, 1) and also by E JEisenbraun et al (Journal of Organic Chemistry, 31, 2716, 1966). Each ofthe products was characterized by proton nuclear magnetic resonancespectroscopy and the spectroscopy data is recorded in Table 4 below.

METHOD B

(i) The indanones were prepared following the general method describedby L I Smith et al (Journal of the American Chemical Society, 73, 3843,1951).

(ii) The indanes were prepared from the corresponding indanonesfollowing the general method described by W E Parham et al (Journal ofthe American Society, 78, 1440, 1956).

Each of the products was characterized by proton nuclear magneticresonance spectroscopy and the spectroscopic data is recorded in Table 4below.

METHOD C

(i) 3-Phenylpropionic acids were prepared following the general methoddescribed by C Kaiser et al (Journal of Medicinal Chemistry, 23(5), 506,1980).

(ii) The indanones were prepared from the appropriate 3-phenylpropionicacids following the general method described by J Koo (Journal of theAmerican Chemical Society, 75, 1819, 1953).

(iii) The indanes were prepared from the corresponding indanonesfollowing essentially the same procedure as that described in Example 1,part (iii).

Each of the products was characterized by proton nuclear magneticresonance spectroscopy and the spectroscopic data is recorded in Table 4below.

                  TABLE 4                                                         ______________________________________                                        Indane Precursors to the Compounds of Formula I                               Indane                       Proton Chemical Shift                            Derivatives                                                                            Method   Appearance δ in ppm (CDCl.sub.3)                      ______________________________________                                        3,3,4,5,7-                                                                             A        Colourless 1.35(6H, s); 1.84(2H, t);                        (CH.sub.3).sub.5  oil        2.12-2.26(6H, m); 2.70                                                        (2H, t); 6.80(1H, s).                            2,3,3,4,5,7-                                                                           A        Colourless 0.80-1.10(7H, m); 1.40                           (CH.sub.3).sub.6  oil        (3H, s); 2.21(3H, s);                                                         2.23(3H, s); 2.25(3H, s);                                                     2.75(2H, d); 6.80(1H, s).                        1,1,4,5,6-                                                                             A        Colourless 0.90(2H, m); 1.24(6H, s);                        (CH.sub.3).sub.5  oil        2.18(6H, s); 2.25(3H, s);                                                     2.90(2H, m); 6.80(1H, s).                        2-CH.sub.3 -5-Br                                                                       C        Colourless 1.10(3H, d); 1.20(1H, m);                                          oil        2.60-3.00(4H, m); 7.00-                                                       7.40(3H, m).                                     2,4,5,7-(CH.sub.3).sub.4                                                               B        Colourless 1.17(4H, m); 2.10(3H, s);                                          oil        2.15(3H, s); 2.20(3H, s);                                                     2.80-3.10(4H, m); 6.77                                                        (1H, s).                                         1,4,5,7-(CH.sub.3).sub.4                                                               B        Colourless 1.10(3H, d); 1.50(2H, m);                                          oil        2.10(3H, s); 2.19(6H, s);                                                     2.60-2.90(2H, m); 3.10-                                                       3.30(1H, m); 6.70(1H, s).                        2,4,5,6- B        Colourless 1.17(4H, m); 1.80(6H, s);                        (CH.sub.3).sub.4  oil        1.20(3H, s); 2.80-3.10                                                        (4H, m); 6.83(1H, s).                            3,4,5,6- B        Colourless 1.10(5H, m); 2.10(3H, s);                        (CH.sub.3).sub.4  oil        2.20(6H, s); 2.60-3.50                                                        (4H, m); 6.83(1H, s).                            ______________________________________                                    

EXAMPLE 6

This Example details the preparation of the indanecarboxaldehydes offormula V which were used in the preparation of the compounds of theinvention of formula I.

METHOD A

The indanecarboxaldehydes were prepared from the correspondingaminoindane following the general method described by W F Beech et al(Journal of the Chemical Society, 1954, page 1297) and S D Jolad et al(Organic Synthesis, Vol 5, page 139). The products were characterized byproton magnetic resonance spectroscopy and the details are recorded inTable 5, below.

METHOD B

The indanecarboxaldehydes were prepared from the correspondingbromoindane following the general method described by G A Olah et al(Angew. Chem. Int. Ed. 20(10), 878, 1981). The products werecharacterized by proton magnetic resonance spectroscopy and the detailsare recorded in Table 5, below.

METHOD C:

The indanecarboxaldehydes were prepared by direct formylation of theindane ring following the general method described by A Rieche et al(Organic Synthesis, Vol 5, page 49). The products were characterized byproton magnetic resonance spectroscopy and the details are recorded inTable 5, below.

                                      TABLE 5                                     __________________________________________________________________________    Indanecarboxaldehyde Precursors to the Compounds of Formula I                  ##STR18##                                                                    Indane-                                                                       carboxaldehyde                Proton Chemical Shift                           (X).sub.m + (W).sub.p                                                                      CHO Method                                                                             Appearance                                                                            δ in ppm (CDCl.sub.3)                     __________________________________________________________________________    H            5-  A    Yellow  1.20(2H, m); 3.00(4H,                                                 oil     m); 7.00-7.80(3H, m);                                                         9.80(1H, s).                                    4,7-(CH.sub.3).sub.2                                                                       5-  C    Pale    1.90-2.20(5H, m); 2.55                                                yellow  (3H, s); 2.70-3.00(4H,                                                solid mp                                                                              m); 7.40(1H, s); 10.20                                                <50° C.                                                                        (1H, s).                                        4,6-(CH.sub.3).sub.2                                                                       5-  B    Yellow  Not recorded                                                          oil                                                     4,6,7-(CH.sub.3).sub.3                                                                     5-  C    Pale    1.80-2.40(5H, m); 2.42                                                yellow  (6H, s); 2.90(4H, m);                                                 solid   10.60(1H, s).                                                         mp 107° C.                                       7-Br-4,6-(CH.sub.3).sub.2                                                                  5-  C    Yellow  1.90-2.20(5H, m); 2.55                                                solid   (3H, s); 2.70-3.00(4H,                                                mp 115° C.                                                                     m); 10.50(1H, s).                               4,6-(CH.sub.3).sub.2                                                                       7-  B    Brown   1.85-2.42(5H, m); 2.60                                                oil     (3H, s); 2.77(2H, t);                                                         3.29(2H, t); 6.87(1H, s);                                                     10.51(1H, s).                                   4,5,6-(CH.sub.3).sub.3                                                                     7-  C    Brown   1.90-2.20(8H, m);                                                     solid   2.60(3H, s); 2.80(2H, t);                                             mp <50° C.                                                                     3.20(2H, t); 10.60                                                            (1H, s).                                        5-Br-4,7-(CH.sub.3).sub.2                                                                  6   C    Yellow  1.90-2.20(2H, m); 2.35                                                solid,  (3H, s); 2.40(3H, s);                                                 mp 115° C.                                                                     2.75-3.00(4H, m); 10.22                                                       (1H, s).                                        4,7-(CH.sub.3).sub.2 -5-C.sub.2 H.sub.5                                                    6   C    Colour- 1.20(3H, t); 1.90-2.20                                                less mp (2H, m); 2.20(3H, s);                                                 <50° C.                                                                        2.40(3H, s); 2.75-3.00                                                        (6H, m); 10.60(1H, s).                          4-Cl-5,7-(CH.sub.3).sub.2                                                                  6   C    Oil     1.85-2.50(5H, m); 2.60                                                        (3H, s); 2.72-3.20                                                            (4H, m); 10.48(1H, s).                          4-Cl-6,7-(CH.sub.3 ).sub.2                                                                 5   C    Bone    1.80-2.52(8H, m); 2.75-                                               solid,  3.16(4H, m); 10.55                                                    mp 108-110° C.                                                                 (1H, s).                                        5-Cl-4,7-(CH.sub.3).sub.2                                                                  6   C    Yellow  1.97-2.40(8H, m); 2.70-                                               solid,  2.90(4H, m); 10.50(1H, s).                                            mp 124° C.                                       5-F-4,6-(CH.sub.3).sub.2                                                                   7   C    Brown   2.20(3H, d); 2.50(3H, d);                                             oil     2.80(2H, t); 3.22(2H, t);                                                     10.40(1H, s).                                   2-CH.sub.3   5   B    Brown   1.10(3H, d); 1.50(1H, m);                                             oil     2.50(2H, m); 3.00(2H, m);                                                     7.20(3H, m); 9.90(1H, s).                       2,2-(CH.sub.3).sub.2                                                                       5   B    Brown   1.10(6H, s); 2.50(2H, s);                                             oil     3.01(2H, s); 7.30(3H, m);                                                     9.90(1H, s).                                    3,3,4,5,7-(CH.sub.3).sub.5                                                                 6   C    Yellow  1.40(6H, s); 1.90(2H, t);                                             oil     2.20(3H, s); 2.40(6H, s);                                                     2.80(2H, t); 10.60(1H, s)                       2,3,3,4,5,7-(CH.sub.3).sub.6                                                               6   C    Brown   1.00(6H, m); 1.40(3H, s);                                             oil     2.00-2.60(11H, m); 2.90                                                       (1H, m); 10.78(1H, s).                          2,4,5,7-(CH.sub.3).sub.4                                                                   6   C    Yellow  1.12(3H, d); 2.10-2.60                                                solid,  (12H, m); 2.80-3.20                                                   mp 50° C.                                                                      (2H, m); 10.60(1H, s).                          1,4,5,7-(CH.sub.3).sub.4                                                                   6   C    Yellow  1.10(3H, d); 1.80-2.20                                                oil     (2H, m); 2.20(3H, s);                                                         2.41(6H, s); 2.80-3.00                                                        (2H, m); 3.40(1H, m);                                                         10.50(1H, s).                                   2,2,4,5,6-(CH.sub.3).sub.5                                                                 7   C    Brown   1.10(6H, s); 2.20(6H, s);                                             oil     2.55(3H, s); 2.62(2H, s);                                                     3.05(2H, s); 10.20(1H, s)                       1,1,4,5,6-(CH.sub.3).sub.5                                                                 7   C    Yellow  1.40(6H, s); 1.90(2H, t);                                             oil     2.19(3H, s); 2.22(3H, s);                                                     2.40(3H, s); 2.80(2H, t);                                                     10.60(1H, s).                                   2,4,5,6-(CH.sub.3).sub.4                                                                   7   C    Brown   1.10(3H, d); 2.20(6H, s);                                             oil     2.50(3H, s); 2.20-2.60                                                        (1H, m); 2.80-3.00(2H,                                                        m); 3.40(2H, m); 10.46                                                        (1H, s).                                        3,4,5,6-(CH.sub.3).sub.4                                                                   7   C    Yellow  1.10(3H, d); 1.90(2H, m);                                             oil     2.20(3H, s); 2.38(6H, s);                                                     2.80(3H, m); 10.65                                                            (1H, s).                                        2,2,4,5,7-(CH.sub.3).sub.5                                                                 6   C    Yellow  1.25(6H, s); 2.13(3H, s);                                             solid,  2.37(3H, s); 2.40(3H, s);                                             mp <50° C.                                                                     2.70(4H, s); 10.60(1H, s)                       2,2,4,7-(CH.sub.3).sub.4                                                                   5   C    Yellow  1.20(6H, s); 2.23(3H, s);                                             oil     2.45(3H, s); 2.70(4H, s);                                                     7.40(1H, s); 10.60(1H, s)                       5-CH.sub.2 CH.sub.2 CH.sub.2 -6                                                            4   C    Yellow  2.00-2.20(4H, m); 2.90                                                solid   (4H, t); 3.20(4H, t);                                                         7.48(1H, s); 10.38(1H, s)                       5-CH.sub.2 CH.sub.2 CH.sub.2 -6-7-CH.sub.3                                                 4   C    Yellow  2.00-2.20(7H, m); 2.80                                                solid,  (4H, t); 3.25(4H, t);                                                 mp <50° C.                                                                     10.20(1H, s).                                   __________________________________________________________________________

EXAMPLE 7

This example details the preparation of thetetrahydronaphthalenecarboxaldehydes and thebenzosuberanecarboxaldehydes of formula V, which were used in thepreparation of the compounds of the invention of formula I. Thecarboxaldehydes were prepared following essentially the same proceduresas that described in Example 6. The products were characterized byproton magnetic resonance spectroscopy and the spectroscopic details arerecorded in Table 6, below.

                  TABLE 6                                                         ______________________________________                                        Tetrahydronaphthalenecarboxaldehyde and Benzosuberane-                        carboxaldehyde Precursors to the Compounds of Formula I                        ##STR19##                                                                                         Meth- Appear-                                                                              Proton Chemical Shift                       (X).sub.m                                                                            CHO     n     od    ance   δ in ppm (CDCl.sub.3)                 ______________________________________                                        2,3,4- 1       2     C     Yellow 1.60-1.80(4H, m); 2.20                      (CH.sub.3).sub.3           solid, (6H, s); 2.40(3H, s);                                                  mp     3.60(2H, m); 4.00(2H, -    51°                                         C. m); 10.55(1H, s).                        2,3,4- 1       3     C     Yellow 1.40-1.60(6H, m); 2.20                      (CH.sub.3).sub.3           solid, (3H, s); 2.30(3H, s);                                                  mp     2.40(3H, s); 2.80-3.00                                                 50° C.                                                                        (4H, m); 10.50(1H, s).                      2-OCH.sub.3 -                                                                        1       2     C     Brown  1.75(4H, m); 2.20(6H,                       3,4-                       oil    s); 2.60(2H, m);                            (CH.sub.3).sub.2                  3.00(2H, m); 3.80(3H,                                                         s); 10.50(1H, s)                            ______________________________________                                    

EXAMPLE 82-[1-(Ethoxyimino)propyl]-3-hydroxy-5-(5-indanyl)cyclohex-2-en-1-one (1)

(i) An aqueous solution of 10% sodium hydroxide (50-70 ml) was addeddropwise over a period of 5 minutes to a suspension ofindane-5-carboxaldehyde (18.50 g; 127 mmole) in acetone (50 ml) andwater (50 ml). The mixture was stirred at a temperature of 65° C. for aperiod of 11/2 hours and then extracted with dichloromethane (200 ml).The organic extract was washed several times with water, dried overanhydrous sodium sulphate, and the solvent was removed under reducedpressure using a rotary evaporator to give 1-(5-indanyl)but-1-en-3-one(19.25 g; 81%) as a viscous oil.

Proton magnetic resonance spectrum (CDCl₃ ; δ in ppm): 2.05 (2H,m); 2.35(3H,s); 2.90 (4H, m); 6.62 (1H, d): 7.10-7.60 (4H, m).

(ii) Diethyl malonate (17.5 g; 110 mmole) was added to a solution ofsodium metal (1.91 g; 83 mmole) in anhydrous absolute ethanol (50 ml)and the mixture was heated to reflux temperature. A mixture of1-(5-indanyl)but-1-en-3-one (19.25 g; 103 mmole) in anhydrous absoluteethanol (50 ml) was added over a period of two minutes and the mixturewas heated under reflux for a period of 2 hours. An aqueous solution ofsodium hydroxide (30% solution, 50 ml) was added and the mixture washeated under reflux for a further 11/2 hours. The solution was pouredinto water (200 ml) and the aqueous mixture was extracted twice withethyl acetate (2×100 ml). The aqueous phase was acidified withconcentrated hydrochloric acid and warmed gently until the evolution ofcarbon dioxide ceased. The aqueous mixture was extracted with ethylacetate, dried over anhydrous sodium sulphate, and the solvent wasremoved by evaporation under reduced pressure using a rotary evaporator.The product, 3-hydroxy-5-(5-indanyl)cyclohex-2-en-1-one, was obtained asa white solid (18.70 g; 79.6%), mp 198° C.

Proton magnetic resonance spectrum (d₆ -dimethyl-sulfoxide; δ in ppm):1.80-3.80 (11H, m); 5.20 (1H, s); 7.00-7.20 (3H, m); 11.8 (1H, broad s).

(iii) METHOD (A)

A mixture of 3-hydroxy-5-(5-indanyl)cyclohex-2-en-1-one (5.0 g; 22mmole) in dichloromethane (100 ml) and pyridine (1.74 g; 22 mmole) wasstirred at room temperature whilst propionyl chloride (1.92 g; 22 mmole)was added dropwise over a period of two minutes. Stirring was continuedfor 1 hour after which the organic solution was washed with water (2×100ml), dried over anhydrous sodium sulphate, and the solvent was removedunder reduced pressure using a rotary evaporator. The resulting brownoil was immediately dissolved in 1,2-dichloroethane (50 ml) and addeddropwise to a mixture of aluminium trichloride (5.85 g; 44 mmole) in1,2-dichloroethane (50 ml) over 30 min at such a rate that thetemperature did not exceed 30° C. After stirring for 30 min at roomtemperature, the solution was poured into 100 ml of a 1:1 mixture ofconcentrated hydrochloric acid and water. The organic solution waswashed with water (2×200 ml), dried over anhydrous sodium sulphate andthe solvent was removed under reduced pressure using a rotaryevaporator. The resulting yellow oil was purified by chromatography oversilica gel (eluant dichloromethane) to give3-hydroxy-5-(5-indanyl)-2-propionylcyclohex-2-en-1-one, (1.71 g; 27%) asa yellow solid, mp 98° C.

Proton magnetic resonance spectrum (CDCl₃ ; δ in ppm): 1.10 (3H, t);2.00 (2H, m); 2.50-3.40 (11H, m); 7.00-7.40 (3H, m); 18.0 (1H, s).

(iii) METHOD (b)

3-Hydroxy-5-(5-indanyl)cyclohex-2-en-1-one (4.0 g; 18 mmole) wasdissolved in a mixture of propionic acid (4 ml) and propionic anhydride(4 ml) at 130° C. under nitrogen. To the resulting clear solution wasadded 8 drops of trifluoromethyl sulphonic acid and the mixture wasallowed to stir at 130° C. under nitrogen for a further 11/2 hours. Themixture was poured into water (500 ml) and stirred until all theanhydride had reacted (approx 30 min). The resulting solid was filteredoff, pressed dry at the pump and then dissolved in dichloromethane andpurified by column chromatography over silica gel (eluantdichloromethane) to give3-hydroxy-5-(5-indanyl)-2-propionylcyclohex-2-en-1-one (1.88 g; 37%), mp98° C.

(iii) METHOD (c)

3-Hydroxy-5-(5-indanyl)cyclohex-2-en-1-one (4.0 g; 18.0 mmole) was addedto a solution of sodium hydride (0.80 g of 60% w/w; 20.0 mmole) in drydimethylformamide (50 ml) under an atmosphere of nitrogen. After 15minutes propionic anhydride (2.6 g; 20.0 mmole) was added and themixture was heated at 110°-120° C. for 2 hours. It was then poured intowater (300 ml) and extracted with diethyl ether (2×100 ml). The etherextracts were dried over anhydrous sodium sulfate and then evaporatedunder reduced pressure to give a yellow oil. Purification by columnchromatography over silica gel (eluent dichloromethane) gave3-hydroxy-5-(5-indanyl)-2-propionylcyclohex-2-en-1-one (2.76 g; 54%) asa yellow solid, mp 98° C.

(iv) Ethoxyamine hydrochloride (0.42 g; 4.1 mmole) and then aqueous 1%sodium hydroxide (17.0 ml) were added to a solution of3-hydroxy-5-(5-indanyl)-2-propionylcyclohex-2-en-one (1.10 g; 3.87mmole) in anhydrous absolute ethanol (200 ml). The mixture was stirredat room temperature for a period of 4 hours and then the ethanol wasremoved by evaporation under reduced pressure using a rotary evaporator.The residue was treated with dichloromethane and the organic phase waswashed twice with dilute aqueous hydrochloric acid and twice with water.The organic phase was dried over anhydrous sodium sulphate and thesolvent was removed by evaporation under reduced pressure to give theproduct,2-[1-(ethoxyimino)propyl]-3-hydroxy-5-(5-indanyl)-cyclohex-2-en-1-one(1.20 g; 94.8%) as a pale yellow oil.

The product was characterized by proton nuclear magnetic resonancespectroscopy and the spectroscopic data is recorded in Table 9, Example30.

EXAMPLE 9

Compounds No 8, 9, 10, 11, 12, 13, 14, 15, 16, 19, 20, 21, 22, 26, 27,46, 47, 48, 52, 54 and 57 (see Tables 1a-1d) were prepared from theappropriate aldehyde derivative (see Examples 6 and 7) followingessentially the same procedure as that outlined in Example 8. Each ofthe products was characterized by proton nuclear magnetic resonancespectroscopy and the spectroscopic data is recorded in Table 9, Example30.

EXAMPLE 102-[1-(Ethoxyimino)butyl]-3-hydroxy-5-(5-indanyl)cyclohex-2-en-1-one (5)

(i) 2-Butyryl-3-hydroxy-5-(5-indanyl)cyclohex-2-en-1-one, a yellow solidmp 92° C., was prepared from 3-hydroxy-5-(5-indanyl)cyclohex-2-en-1-oneand butyric anhydride following essentially the same procedure as thatdescribed in Example 8, part (iii) Method (b) and Method (c).

(ii)2-[1-(Ethoxyimino)butyl]-3-hydroxy-5-(5-indanyl)cyclohex-2-en-1-one, ayellow oil, was prepared from2-butyryl-3-hydroxy-5-(5-indanyl)cyclohex-2-en-1-one and ethoxyaminehydrochloride in 86.1% yield following essentially the same procedure asthat described in Example 8 part (iv).

The product was characterized by proton nuclear magnetic resonancespectroscopy and the spectroscopic data is recorded in Table 9 Example30.

EXAMPLE 11

Compounds No 23, 24, 34, 49, 50, 51, 53, 55, 56, 58, 59, 60 and 61 (seeTables 1a and 1b) were prepared from the appropriate3-hydroxy-5-(substituted indanyl)cyclohex-2-en-1-one (see Example 28),butyric anhydride and ethoxyamine hydrochloride following essentiallythe same procedure as that described in Example 10. Each of the productswas characterized by proton nuclear magnetic resonance spectroscopy andthe spectroscopic data is recorded in Table 9, Example 30.

EXAMPLE 12

Compounds No 4, 6, 39 and 44 (see Tables 1a and 1b) were prepared fromthe appropriate 2-alkanoyl-3-hydroxy-5-(substitutedindanyl)cyclohex-2-en-1-one (see Example 29) and the appropratehydroxyamine hydrochloride derivative following essentially the sameprocedure as that described in Example 8, part (iv). Each of theproducts was characterized by proton nuclear magnetic resonancespectroscopy and the spectroscopic data is recorded in Table 9, Example30.

EXAMPLE 13 Sodium salt of2-[1-(ethoxyimino)propyl]-3-hydroxy-5-(5-indanyl)cyclohex-2-en-1-one (2)

2-[1-(Ethoxyimino)propyl]-3-hydroxy-5-(5-indanyl)cyclohex-2-en-1-one,(0.31 g; 0.95 mmole) was dissolved in acetone (20 ml) and aqueous 1%sodium hydroxide (3.8 ml) was added in one portion. The mixture wasallowed to stir at room temperature for 10 min and then the acetone wasremoved under reduced pressure on a rotary evaporator. Toluene (50 ml)was added and was similarly removed by distillation. A further twoaliquots of toluene were added and then distilled off to give2-[1-(ethoxyimino)propyl]-3-hydroxy-5-(5-indanyl)cyclohex-2-en-1-onesodium salt as a pale yellow solid, mp<250° C.

EXAMPLE 14

Compounds No 31, 33 and 35 were prepared from compounds No 61, 60 and 34(see Table 1b) and sodium hydroxide following essentially the sameprocedure as that described in Example 13. The products may beidentified by their melting points which are recorded in Table 9,Example 30.

EXAMPLE 153-Benzoyl-2-[1-(ethoxyimino)propyl]-5-(5-indanyl)cyclohex-2-en-1-one (3)

The sodium salt of2-[1-(ethoxyimino)propyl]-3-hydroxy-5-(5-indanyl)cyclohex-2-en-1-one(0.95 mmole) was dissolved in acetone (50 ml) and benzoyl chloride (0.13g; 0.95 mmole) was added dropwise over a period of 2 minutes. Themixture was stirred at room temperature for 5 minutes, then filtered andevaporated under reduced pressure to give3-benzoyl-2-[1-(ethoxyimino)propyl]-5-(5-indanyl)cyclohex-2-en-1-one(0.31 g; 75.7%) as a yellow oil.

The product was characterized by proton nuclear magnetic resonancespectroscopy and the spectroscopic data is recorded in Table 9, Example30.

EXAMPLE 16

Compounds Nos 32, 37, 38 and 42 were prepared from the sodium salt of2-[1-(ethoxyimino)butyl]-3-hydroxy-5-(5,6,7-trimethyl-4-indanyl)cyclohex-2-en-1-one(31) and the appropriate acid chloride following essentially the sameprocedure as that described in Example 15. Each of the products wascharacterized by proton nuclear magnetic resonance spectroscopy and thespectroscopic data is recorded in Table 9, Example 30.

EXAMPLE 17 Copper salt of2-[1-(ethoxyimino)butyl]-3-hydroxy-5-(5,6,7-trimethyl-4-indanyl)cyclohex-2-en-1-one(40)

2-[1(Ethoxyimino)butyl]-3-hydroxy-5-(5,6,7-trimethyl-4-indanyl)cyclohex-2-en-1-one(61), (500 mg, 1.3 mmole) in diethyl ether (50 ml) was shaken with asaturated aqueous cupric acetate solution (50 ml). The mixture was thenevaporated to dryness under reduced pressure. The solid residue waswashed successively with hot water, cooled water and diethyl ether, thendried to give the copper salt of2-[1-(ethoxyimino)butyl]-3-hydroxy-5-(5,6,7-trimethyl-4-indanylcyclohex-2-en-1-one(450 mg, 84%) as a pale green solid, mp 212° C.

EXAMPLE 18 Nickel salt of2-[1-(ethoxyimino)butyl]-2-hydroxy-5-(5,6,7-trimethyl-4-indanyl)cyclohex-2-en-1-one(41)

Compound No 41 was prepared from compound No 61 following an analogousprocedure to that described in Example 17. The product was obtained as asolid and its melting point is recorded in Table 9, Example 30.

EXAMPLE 19 Lithium salt of2-[1-(ethoxyimino)butyl]-3-hydroxy-5-(5,6,7-trimethyl-4-indanyl)cyclohex-2-en-1-one(36)

To a solution of2-[1-(ethoxyimino)butyl]-3-hydroxy-5-(5,6,7-trimethyl-4-indanyl)cyclohex-2-en-1-one(61), (0.50 g; 1.3 mmole) in methanol (30 ml) was added a solution oflithium metal (9.0 mg, 1.3 mmole) dissolved in methanol (2 ml). Themixture was stirred for 15 minutes at room temperature and thenevaporated to dryness under reduced pressure, to give the lithium saltof2-[1-(ethoxyimino)butyl]-3-hydroxy-5-(5,6,7-trimethyl-4-indanyl)cyclohex-2-en-1-one(0.40 g; 78.0%) as a colourless solid, mp<250° C.

EXAMPLE 20 Tetrabutylammonium salt of2-[1-ethoxyimino)butyl]-3-hydroxy-5-(5,6,7-trimethyl-4-indanyl)cyclohex-2-en-1-one(43)

To a solution of2-[1-(ethoxyimino)butyl]-3-hydroxy-5-(5,6,7-trimethyl-4-indanyl)cyclohex-2-en-1-one(0.63 g; 1.6 mmole) in methanol (5 ml) was added a 25% methanolicsolution of tetra-n-butyl ammonium hydroxide (2.0 ml). The mixture waskept at room temperature for 3 hours and then evaporated to drynessunder reduced pressure using a rotary evaporator. The residue was takenup in dichloromethane (15 ml) and water (15 ml). The layers wereseparated and the organic layer washed with water (2×10 ml), dried overanhydrous sodium sulfate and evaporated under reduced pressure to affordthe tetrabutylammonium salt of2-[1-(ethoxyimino)butyl]-3-hydroxy-5-(5,6,7-trimethyl-4-indanyl)cyclohex-2-en-1-one(0.56 g) as a yellow oil. The product was characterized by protonnuclear magnetic resonance spectroscopy and the spectroscopic data isreported in Table 9, Example 30.

EXAMPLE 215-(4,6-Dimethyl-7-N,N-dimethylsulfamoyl-5-indanyl)-2-[1-(ethoxyimino)propyl]-3-hydroxy-cyclohex-2-en-1-one(17)

(i) 5-(4,6-Dimethyl-5-indanyl)-2-propionylcyclohex-2-en-1-one (1.55 g;4.8 mmole) in dichloromethane (12 ml) was cooled to 0° C. andchlorosulfonic acid (5.5 ml) was added dropwise. The temperature wasmaintained at 0° C. for a further 30 minutes, after which the mixturewas allowed to warm to room temperature. The mixture was poured ontocracked ice and the organic layer separated, dried over anhydrousmagnesium sulfate and evaporated to give5-(7-chlorosulfonyl-4,6-dimethyl-5-indanyl)-3-hydroxy-2-propionylcyclohex-2-en-1-one(1.60 g; 81.0%) as a brown solid, which was used without furtherpurification.

(ii) To a solution of water (35 ml) and 33% ethanolic dimethylamine (35ml) at 0° C. was added5-(7-chlorosulfonyl-4,6-dimethyl-5-indanyl)-3-hydroxy-2-propionylcyclohex-2-en-1-one(1.60 g; 3.9 mmole). The reaction was stirred at 0° C. for 30 minutesand then allowed to come to room temperature. The mixture was acidifiedwith dilute hydrochloric acid, extracted with dichloromethane, driedover anhydrous magnesium sulfate and evaporated under reduced pressureto give5-(4,6-dimethyl-7-N,N-dimethylsulfamoyl-5-indanyl)-3-hydroxy-2-propionylcyclohex-2-en-1-one(1.40 g; 86.0%) as a yellow oil. The product was characterized by protonnuclear magnetic resonance spectroscopy and the spectroscopic data isrecorded in Table 8, Example 29.

(iii)5-(4,6-Dimethyl-7-N,N-dimethylaminosulfamoyl-5-indanyl)-2-[1-(ethoxyimino)propyl]-3-hydroxycyclohex-2-en-1-one(17) was prepared from5-(4,6-dimethyl-7-N,N-dimethylaminosulfamoyl-5-indanyl)-3-hydroxy-2-propionylcyclohex-2-en-1-one,following an analogous procedure to that described in Example 8, part(iv). The product was characterized by proton nuclear magnetic resonancespectroscopy and the spectroscopic data is recorded in Table 9, Example30.

EXAMPLE 22

Compound No 18 was prepared from5-(4,7-dimethyl-5-indanyl)-3-hydroxy-2-propionylcyclohex-2-en-1-one (seeExample 29) by essentially the same procedure as that outlined inExample 21. The product was characterized by proton nuclear magneticresonance spectroscopy and the spectroscopic data is recorded in Table9, Example 30.

EXAMPLE 235-(6-Chloro-4,7-dimethyl-5-indanyl)-2-[1-(ethoxyimino)benzyl]-3-hydroxycyclohex-2-en-1-one(25)

(i) 5-(6-Chloro-4,7-dimethyl-5-indanyl)-3-hydroxycyclohex-2-en-1-one(see Example 28) (1.40 g; 4.8 mmole) was dissolved in ethanol (50 ml)and sodium bicarbonate (0.45 g; 5.3 mmole) dissolved in water (20 ml)was added. The mixture was stirred until the evolution of carbon dioxidehad ceased and then the solvent was removed under reduced pressure. Thedried solid was dissolved in dimethylformamide (50 ml) and heated to110° C. Benzoic anhydride (1.19 g; 5.3 mmole) dissolved indimethylformide (10 ml) was added and the mixture was stirred at 110° C.for 2 hours. The solvent was removed under reduced pressure and theresidue purified by column chromatography over silica gel (eluantdichloromethane) to give2-benzoyl-5-(6-chloro-4,7-dimethyl-5-indanyl)-3-hydroxy-cyclohex-2-en-1-one(0.43 g; 23.0%) as a yellow oil. The product was characterized by protonnuclear magnetic resonance spectroscopy and the spectroscopic data isrecorded in Table 8, Example 29.

(ii)5-(6-Chloro-4,7-dimethyl-5-indanyl)-2-[1-(ethoxyimino)benzyl]-3-hydroxy-cyclohex-2-en-1-oneand ethoxyamine hydrochloride following essentially the same procedureas that described in Example 8, part (iv). The product was characterizedby proton nuclear magnetic resonance spectroscopy and the spectroscopicdata is recorded in Table 9, Example 30.

EXAMPLE 24

Compound No 45 was prepared from3-hydroxy-5-(5,6,7-trimethyl-4-indanyl)cyclohex-2-en-1-one (see Example28) by an analogous method to that described in Example 23. The productwas characterized by proton nuclear magnetic resonance spectroscopy andthe spectroscopic data is recorded in Table 9, Example 30.

EXAMPLE 252-[1-(Ethoxyimino)propyl]-3-hydroxy-5-(5,6,7,8-tetrahydro-2-naphthyl)cyclohex-2-en-1-one(7)

(i) 1-(5,6,7,8-Tetrahydro-2-naphthyl)but-1-en-3-one, a yellow oil, wasprepared from 5,6,7,8-tetrahydro-2-naphthaldehyde and acetone in 63%yield following essentially the same procedure as that described inExample 8, part (i).

Proton magentic resonance spectrum (CDCl₃ ; δ in ppm): 1.65 (4H m); 2.30(3H, s); 2.70 (4H, m); 6.60 (1H, d); 7.00-7.30 (3H, m); 7.40 (1H, d).

(ii) 3-Hydroxy-5-(5,6,7,8-tetrahydro-2-naphthyl)cyclohex-2-en-1-one, apale yellow solid mp 198° C., was prepared from1-(5,6,7,8-tetrahydro-2-naphthyl)-but-1-en-3-one in 48.3% yieldfollowing essentially the same procedure as that described in Example 8part (ii).

(iii) 3-Hydroxy-5-(5,6,7,8-tetrahydro-2-naphthyl)cyclohex-2-en-1-one(2.6 g; 11.0 mmole) was added to a solution of sodium hydride (0.47 g of60% w/w; 12.0 mmole) in dry dimethylformamide (10 ml) under anatmosphere of nitrogen. The mixture was stirred under nitrogen until asolution had been obtained and propionic anhydride was added dropwiseand the mixture was heated to 120° C. The mixture was stirred at 120° C.under nitrogen for a period of 2 hours and then the solvent wasevaporated under reduced pressure. The mixture was treated withdichloromethane (20 ml) and the soluble portion of the residue waschromatrographed over silica gel (eluant dichloromethane) to give3-hydroxy-2-propionyl-5-(5,6,7,8-tetrahydro-2-naphthyl)cyclohex-2-en-1-one(0.86 g; 26.2%) as a yellow solid, mp 87° C.

(iv)2-[1-(Ethoxyimino)propyl]-3-hydroxy-5-(5,6,7,8-tetrahydro-2-naphthyl)cyclohex-2-en-1-one,a yellow oil, was prepared from3-hydroxy-2-propionyl-5-(5,6,7,8-tetrahydro-2-naphthyl)cyclohex-2-en-1-oneand ethoxyamine hydrochloride in 57.3% yield following essentially thesame procedure as that described in Example 8 part (iv).

The product was characterized by proton nuclear magnetic resonancespectroscopy and the spectroscopic data is recorded in Table 9, Example30.

EXAMPLE 26

Compounds No 27, 28 and 30 (see Table 1c) were prepared from theappropriate 3-hydroxy-5-(substituted5,6,7,8-tetrahydro-1-naphthyl)cyclohex-2-en-1-one (see Example 28) andthe appropriate carboxylic anhydride and ethoxyamine hydrochloridefollowing essentially the same procedure as that described in Example25. Each of the products was characterized by proton nuclear magneticresonance spectroscopy and the spectroscopic data is recorded in Table9, Example 30.

EXAMPLE 27

Compound No 29 (see Table 1e) was prepared from3-hydroxy-5-(2,3,4-trimethyl-1-benzosuberanyl)cyclohex-2-en-1-one (seeExample 28), propionic anhydride and ethoxyamine hydrochloride followingessentially the same procedure as that described in Example 25. Theproduct was characterized by proton nuclear magnetic resonancespectroscopy and the spectroscopic data is recorded in Table 9, Example30.

EXAMPLE 28

The 5-arylcyclohexane-1,3-diones of formula IX used in the preparationof the compounds of formula I were prepared from the appropriatearylaldehyde derivative following essentially the same procedure as thatdescribed in Example 8 parts (i) and (ii).

The majority of the 5-arylcyclohexane-1,3-diones of formula IX wereobtained as solids and were characterized by their nuclear magneticresonance spectra. For convenience, proton nuclear magnetic resonancespectroscopic (pmr) data and/or melting point data is recorded in Table7 below.

                  TABLE 7a                                                        ______________________________________                                         ##STR20##                                                                                          Proton Chemical Shift                                   (X).sub.m + (W).sub.p                                                                   Appearance  δ in ppm (D.sub.6 -DMSO)                          ______________________________________                                        H         Pale yellow 1.80-3.80(11H, m); 5.20                                           solid, mp   (1H, s); 7.00-7.20(3H, m);                                        198° C.                                                                            11.80(1H, s).                                           4,7-(CH.sub.3).sub.2                                                                    Yellow solid,                                                                             1.75-2.18(8H, m); 2.20-                                           mp 184° C.                                                                         3.60(9H, m); 5.25(1H, s);                                                     6.90(1H, s); 11.00(1H, s).                              4,6-(CH.sub.3).sub.2                                                                    Yellow solid                                                                              2.00(2H, m); 2.12-2.20(6H,                                                    m); 2.20-3.40(8H, m); 3.95                                                    (1H, m); 5.80(1H, s); 6.55                                                    (1H, s); 11.00(1H, s).                                  7-Br-4,6-(CH.sub.3).sub.2                                                               Yellow      2.00(2H, m); 2.20(3H, s);                                         solid       2.40(3H, s); 2.40-3.45                                                        (8H, m); 3.95(1H, m); 5.30                                                    (1H, s); 11.00(1H, s).                                  2,2,4,7-(CH.sub.3).sub.4                                                                Colourless  Not recorded                                                      solid, mp                                                                     245° C.                                                      2,2,4,6,7-(CH.sub.3).sub.5                                                              Yellow solid                                                                              1.10(6H, s); 2.10(3H, s);                                                     2.20(6H, s); 2.40-3.00                                                        (8H, m); 3.70(1H, m); 5.27                                                    (1H, s); 11.00(1H, s).                                  2,2-(CH.sub.3).sub.2                                                                    Yellow solid,                                                                             not recorded                                                      mp 170° C.                                                   6-Br-4,7-(CH.sub.3).sub.2                                                               Yellow solid                                                                              2.00(2H, m); 2.20(3H, s);                                                     2.30(3H, s); 2.38-3.40                                                        (8H, m); 3.90(1H, m); 5.50                                                    (1H, s); 11.10(1H, s).                                  4,7-(CH.sub.3).sub.2 -6-                                                                Yellow solid,                                                                             Not recorded                                            C.sub.2 H.sub.5                                                                         mp 254° C.                                                   7-Cl-4,6- Yellow solid                                                                              1.75-4.10(17H, m); 5.28                                 (CH.sub.3).sub.2      (1H, s); 11.20(1H, s).                                  4-Cl-6,7- Cream solid,                                                                              Not recorded                                            (CH.sub.3).sub.2                                                                        mp 226-230° C.                                               6-Cl-4,7- Cream solid,                                                                              Not recorded                                            (CH.sub.3).sub.2                                                                        mp 227° C.                                                   2-CH.sub.3                                                                              Yellow solid,                                                                             Not recorded                                                      mp 204° C.                                                   1,1,4,6,7-                                                                              Tan solid,  Not recorded                                            (CH.sub.3).sub.5                                                                        mp >250° C.                                                  1,1,2,4,6,7-                                                                            Cream solid,                                                                              Not recorded                                            (CH.sub.3).sub.6                                                                        mp 270° C.                                                   3,4,6,7-  Colourless  Not recorded                                            (CH.sub.3).sub.4                                                                        solid, mp                                                                     232° C.                                                      2,4,6,7-  Cream solid,                                                                              Not recorded                                            (CH.sub.3).sub.4                                                                        mp 213°  C.                                                  4,6,7-(CH.sub.3).sub.3                                                                  Yellow solid,                                                                             1.80-2.40(11H, m); 2.45-                                          mp 221° C.                                                                         4.00(9H, m); 5.35(1H, s);                                                     11.00(1H, s).                                           ______________________________________                                    

                  TABLE 7b                                                        ______________________________________                                         ##STR21##                                                                                           Proton Chemical Shift                                  (X).sub.m + (W).sub.p                                                                     Appearance δ in ppm (D.sub.6 -DMSO)                         ______________________________________                                        5,7-(CH.sub.3).sub.2                                                                      Yellow solid                                                                             1.80-2.40(8H, m); 2.45-                                                       3.00(8H, m); 3.40(1H, m);                                                     5.45(1H, s); 6.75(1H, s);                                                     11.00(1H, s).                                          5,6,7-(CH.sub.3).sub.3                                                                    Yellow solid,                                                                            1.80-2.20(11H, m); 2.20-                                           mp 179° C.                                                                        3.00(4H, m); 3.40-3.80                                                        (5H, m); 5.20(1H, s); 11.00                                                   (1H, s).                                               6-Cl-5,7-   Yellow solid,                                                                            Not recorded                                           (CH.sub.3).sub.2                                                                          mp 160° C.                                                 6-F-5,7-(CH.sub.3).sub.2                                                                  Colourless Not recorded                                                       solid                                                             2,2,5,6,7-  Colourless Not recorded                                           (CH.sub.3).sub.5                                                                          solid, mp                                                                     246° C.                                                    3,3,5,6,7-  Yellow solid                                                                             1.40(6H, s); 1.90(2H, t);                              (CH.sub.3).sub.5       2.16(3H, s); 2.19(3H, s);                                                     2.50-3.40(6H, m); 3.99                                                        (1H, m); 5.30(1H, s); 11.05                                                   (1H, s).                                               2,5,6,7-(CH.sub.3).sub.4                                                                  Colourless Not recorded                                                       solid, mp                                                                     221° C.                                                    1,5,6,7-(CH.sub.3).sub.4                                                                  Colourless Not recorded                                                       solid, mp                                                                     191° C.                                                    5-CH.sub.2 CH.sub.2 CH.sub.2 -6                                                           Brownish   1.90-2.30(7H, m); 2.50-                                            solid      3.00(12H, m); 3.40(1H, m);                                                    5.30(1H, s); 11.00(1H, s).                             7-CH.sub.3 -5-                                                                            Cream      Not recorded                                           CH.sub.2 CH.sub.2 CH.sub.2 -6                                                             solid,                                                                        mp 214° C.                                                 5-Br-6,7-   Light brown                                                                              1.88-4.28(11H, m); 2.24                                (CH.sub.3).sub.2                                                                          solid      (3H, s); 2.39(3H, s);                                                         5.31(1H, s); 11.20(1H, s).                             ______________________________________                                    

                  TABLE 7c                                                        ______________________________________                                         ##STR22##                                                                                          Proton Chemical Shift                                   (X).sub.m + (W).sub.p                                                                   Appearance  δ in ppm (D.sub.6 -DMSO)                          ______________________________________                                        2,3,4-(CH.sub.3).sub.3                                                                  Colourless  1.60-1.80(4H, m); 2.10(6H,                                        solid, mp   s); 2.20(3H, s); 2.30-                                            214° C.                                                                            3.30(8H, m); 3.80(1H, m);                                                     5.30(1H, s); 11.00(1H, s).                              3,4-(CH.sub.3).sub.2 -2-                                                                Brown solid 1.70(4H, m); 2.10(3H, s);                               OCH.sub.3             2.20(3H, s); 2.40-3.30                                                        (8H, m); 3.70(3H, s); 5.25                                                    (1H, s); 11.00(1H, s).                                  ______________________________________                                    

                  TABLE 7d                                                        ______________________________________                                         ##STR23##                                                                                             Proton Chemical Shift                                (X).sub.m + (W).sub.p                                                                     Appearance   δ in ppm (D.sub.6 -DMSO)                       ______________________________________                                        H           Pale yellow  Not recorded                                                     solid, mp                                                                     198° C.                                                    ______________________________________                                    

                  TABLE 7e                                                        ______________________________________                                         ##STR24##                                                                                           Proton Chemical Shift                                  (X).sub.m + (W).sub.p                                                                    Appearance  δ in ppm (D.sub.6 -DMSO)                         ______________________________________                                        2,3,4-(CH.sub.3).sub.3                                                                   Orange solid                                                                              1.40(6H, m); 2.18(6H, s);                                                     2.21(3H, s); 2.25-3.40(8H,                                                    m); 3.98(1H, m); 5.20(1H,                                                     s); 11.00(1H, s).                                      ______________________________________                                    

EXAMPLE 29

The 2-acyl-5-arylcyclohexane-1,3-dione derivatives of formula XIII usedin the preparation of the compounds of formula I were prepared from thecorresponding 5-arylcyclohexane-1,3-dione derivatives of formula IX byacylation using the appropriate acyl derivative and following aprocedure essentially the same as that described in Example 8 part(iii).

The majority of the 2-acyl-5-arylcyclohexane-1,3-dione derivatives offormula XIII were obtained as oils and were characterized by theirnuclear magnetic resonance spectra. For convenience, proton nuclearmagnetic resonance spectroscopic (pmr) data and/or melting point data isrecorded in Table 8 below.

                  TABLE 8a                                                        ______________________________________                                         ##STR25##                                                                                                  Proton Chemical                                                               Shift δ in ppm                            (X).sub.m + (W).sub.p                                                                   R.sup.3  Appearance (CDCl.sub.3)                                    ______________________________________                                        H         C.sub.2 H.sub.5                                                                        Yellow solid,                                                                            1.10(3H, t); 2.00(2H,                                              mp 98° C.                                                                         m); 2.50-3.40(11H, m);                                                        7.00-7.40(3H, m);                                                             18.00(1H, s).                                   H         n-C.sub.3 H.sub.7                                                                      Yellow solid,                                                                            1.17(3H, t); 1.65(2H,                                              mp 92° C.                                                                         m); 2.06(2H, m); 2.68-                                                        3.21(11H, m); 6.95-                                                           7.14(3H, m); 18.00(1H,                                                        s).                                             4,7-(CH.sub.3).sub.2                                                                    C.sub.2 H.sub.5                                                                        Yellow oil 1.15(3H, t); 1.90-                                                            2.20(8H, m); 2.60-                                                            3.20(10H, m); 3.50                                                            (1H, m); 6.80(1H, s);                                                         18.20(1H, s).                                   4,6-(CH.sub.3).sub.2                                                                    C.sub.2 H.sub.5                                                                        Yellow oil 1.20(3H, t); 1.95-                                                            2.40(8H, m); 2.40-                                                            3.30(10H, m); 3.80(1H,                                                        m); 6.90(1H, s);                                                              18.20(1H, s).                                   4,6,7-(CH.sub.3).sub.3                                                                  C.sub.2 H.sub.5                                                                        Yellow oil 1.10(3H, t); 1.80-                                                            2.30(11H, m); 2.40-                                                           3.60(10H, m); 3.90(1H,                                                        m); 18.10(1H, s).                               7-Br-4,6- C.sub.2 H.sub.5                                                                        Yellow oil 1.15(3H, t); 2.00-2.80                          (CH.sub.3).sub.2              (8H, m); 2.80-3.40                                                            (10H, m); 3.80(1H, m);                                                        18.10(1H, s).                                   2,2,4,7-  C.sub.2 H.sub.5                                                                        Orange oil 1.00-1.25(9H, m); 2.14                          (CH.sub.3).sub.4              (6H, s); 2.40-2.90(8H,                                                        m); 3.10(2H, q); 3.65                                                         (1H, m); 6.78(1H, s);                                                         18.20(1H, s).                                   2,2,4,6,7-                                                                              C.sub.2 H.sub.5                                                                        Yellow oil 1.05-1.25(9H, m); 2.10                          (CH.sub.3).sub.5              (3H, s); 2.20(6H, s);                                                         2.20-3.40(10H, m);                                                            3.80(1H, m); 18.10                                                            (1H, s).                                        2,2-(CH.sub.3).sub.2                                                                    C.sub.2 H.sub.5                                                                        Yellow oil 1.00-1.25(9H, m);                                                             2.60-3.40(11H, m);                                                            6.80-7.20(3H, m);                                                             18.20(1H, s).                                   4,6-(CH.sub.3).sub.2 -                                                                  C.sub.2 H.sub.5                                                                        Yellow oil 1.12(3H, t); 1.80-                              7-SO.sub.2 N(CH.sub.3).sub.2  2.25(4H, m); 2.32(3H,                                                         s); 2.55-3.52(17H, m);                                                        3.60-4.15(1H, m);                                                             18.25(1H, s).                                   4,7-(CH.sub.3).sub.2 -6-                                                                C.sub.2 H.sub.5                                                                        Yellow oil 1.12(3H, t); 1.90-2.25                          SO.sub.2 N(CH.sub.3).sub.2    (2H, m); 2.40(3H, s);                                                         2.55(3H, s); 2.72(6H,                                                         s); 2.80-3.32(6H, m);                                                         3.70(2H, q); 4.52-4.95                                                        (1H, m); 18.20(1H, s).                          6-Br-4,7- C.sub.2 H.sub.5                                                                        Yellow oil 1.20(3H, t); 1.95-3.25                          (CH.sub.3).sub.2              (18H, m); 3.95(1H, m);                                                        18.20(1H, s).                                   4,7-(CH.sub.3).sub.2 -                                                                  C.sub.2 H.sub.5                                                                        Yellow oil 1.00-1.27(6H, m); 2.80                          6-C.sub.2 H.sub.5             (2H, m); 2.20(3H, s);                                                         2.30(3H, s); 2.40-3.30                                                        (12H, m); 3.80(1H, m);                                                        18.20(1H, s).                                   7-Cl-4,6- C.sub.2 H.sub.5                                                                        Yellow oil 1.15(3H, t); 1.80- 2.35                         (CH.sub.3).sub.2              (5H, m); 2.45(3H, s);                                                         2.55-3.52(10H, m);                                                            3.72-4.12(1H, m);                                                             18.20(1H, s).                                   4-Cl-6,7- C.sub.2 H.sub.5                                                                        Yellow solid,                                                                            Not recorded                                    (CH.sub.3).sub.2   mp 120° C.                                          6-Br-4,7- n-C.sub.3 H.sub.7                                                                      Orange oil 1.00(3H, t); 1.60(2H,                           (CH.sub.3).sub.2              m); 1.95-3.25(18H, m);                                                        3.95(1H, m); 18.20                                                            (1H, s).                                        6-Cl-4,7- n-C.sub.3 H.sub.7                                                                      Orange oil 1.00(3H, t); 1.70(2H,                           (CH.sub.3).sub.2              m); 1.95-3.20(18H, m);                                                        3.95(1H, m); 18.10(1H,                                                        s).                                             6-Cl-4,7- C.sub.6 H.sub.5                                                                        Yellow oil 2.00(2H, m); 2.25(6H,                           (CH.sub.3).sub.2              s); 2.40-3.40(9H, m);                                                         7.40(5H, m); 17.00(1H,                                                        s).                                             2-CH.sub.3                                                                              C.sub.2 H.sub.5                                                                        Yellow oil 1.00-1.15(6H, m);                                                             2.30-3.40(12H, m);                                                            6.80-7.40(3H, m);                                                             18.20(1H, s).                                   1,1,4,6,7-                                                                              C.sub.2 H.sub.5                                                                        Orange oil 1.10(3H, t); 1.38(6H,                           (CH.sub.3).sub.5              s); 1.90(2H, t); 2.20                                                         (9H, s); 2.40-3.40(8H,                                                        m); 3.80(1H, m); 18.20                                                        (1H, s).                                        1,1,2,4,6,7-                                                                            C.sub.2 H.sub.5                                                                        Yellow oil 1.00-1.20(9H, m); 1.40                          (CH.sub.3).sub.6              (3H, s); 2.00(1H, m);                                                         2.25(9H, s); 2.25-3.40                                                        (8H, m); 3.80(1H, m);                                                         18.30(1H, s).                                   1,1,2,4,6,7-                                                                            n-C.sub.3 H.sub.7                                                                      Orange oil 1.00-1.10(9H, m);                               (CH.sub.3).sub.6              1.40(3H, s); 1.70(3H,                                                         m); 2.20(9H, s); 2.20-                                                        3.50(8H, m); 3.85(1H,                                                         m); 18.30(1H, s).                               3,4,6,7-  n-C.sub.3 H.sub.7                                                                      Orange oil 1.00-1.20(6H, m);                               (CH.sub.3).sub.4              1.50-1.80(3H, m);                                                             2.00-3.40(19H, m);                                                            3.80(1H, m); 18.30(1H,                                                        s).                                             2,4,6,7-  n-C.sub.3 H.sub.7                                                                      Orange oil 1.00(3H, t); 1.14(3H,                           (CH.sub.3).sub.4              d); 1.70(2H, m); 2.10                                                         (3H, s); 2.20(3H, s);                                                         2.20-3.40(11H, m);                                                            3.85(1H, m); 18.30                                                            (1H, s).                                        ______________________________________                                    

                  TABLE 8b                                                        ______________________________________                                         ##STR26##                                                                                                  Proton Chemical                                                               Shift δ in ppm                            (X).sub.m + (W).sub.p                                                                    R.sup.3 Appearance (CDCl.sub.3)                                    ______________________________________                                        5,7-(CH.sub.3).sub.2                                                                     C.sub.2 H.sub.5                                                                       Orange oil 1.20(3H, t); 1.90-                                                            2.40(8H, m); 2.50-                                                            3.20(10H, m); 3.60                                                            (1H, m); 6.80(1H, s);                                                         18.10(1H, s).                                   5,6,7-(CH.sub.3).sub.3                                                                   C.sub.2 H.sub.5                                                                       Orange oil 1.20(3H, t); 1.95-                                                            2.20(11H, m); 2.60-                                                           3.30(10H, m); 3.70                                                            (1H, m); 18.20(1H, s).                          6-Cl-5,7-  C.sub.2 H.sub.5                                                                       Pale yellow                                                                              1.20(3H, t); 1.85-                              (CH.sub.3).sub.2   solid, mp  2.35(5H, m); 2.45(3H,                                              <50°  C.                                                                          s); 2.52-3.35(10H, m);                                                        3.52-4.10(1H, m);                                                             18.22(1H, s).                                   6-F-5,7-   n-C.sub.3 H.sub.7                                                                     Yellow oil 1.00(3H, t); 1.60(2H,                           (CH.sub.3).sub.2              m); 1.90-2.20(8H, m);                                                         2.50-3.40(10H, m);                                                            3.60(1H, m); 18.30(1H,                                                        s).                                             5,6,7-(CH.sub.3).sub.3                                                                   C.sub.6 H.sub.5                                                                       Yellow oil 2.00(2H, m); 2.20(6H,                                                         s); 2.30(3H, s); 2.30-                                                        3.40(8H, m); 3.85(1H,                                                         m); 7.50(5H, m);                                                              17.00(1H, s).                                   2,2,5,6,7- C.sub.2 H.sub.5                                                                       Orange oil 1.00-1.20(9H, m);                               (CH.sub.3).sub.5              2.10(6H, s); 2.20(3H,                                                         s); 2.40-3.20(10H, m);                                                        3.70(1H, m); 18.20                                                            (1H, s).                                        2,2,5,6,7- n-C.sub.3 H.sub.7                                                                     Yellow oil 1.00(3H, t); 1.16(6H,                           (CH.sub.3).sub.5              s); 1.60(2H, m); 2.18                                                         (3H, s); 2.20(3H, s);                                                         2.25(3H, s); 2.40-                                                            3.20(10H, m); 3.70                                                            (1H, m); 18.20(1H, s).                          2,2,5,6,7- C.sub.2 H.sub.5                                                                       Yellow oil 1.00-1.40(6H, m);                               (CH.sub.3).sub.5              1.87(2H, t); 2.20(6H,                                                         s); 2.30(3H, s); 2.60-                                                        3.40(8H, m); 3.95(1H,                                                         m); 18.20(1H, s).                               2,5,6,7-   n-C.sub.3 H.sub.7                                                                     Orange oil 1.00(3H, t); 1.15(3H,                           (CH.sub.3).sub.4              d); 1.70(2H, d); 2.20                                                         (6H, s); 2.20-3.30                                                            (11H, m); 2.23(3H, s);                                                        3.79(1H, m); 18.30(1H,                                                        s).                                             1,5,6,7-   n-C.sub.3 H.sub.7                                                                     Orange oil 1.10-1.20(6H, m);                               (CH.sub.3).sub.4              1.60-1.90(4H, m);                                                             2.18(3H, s); 2.20(3H,                                                         s); 2.21(3H, s);                                                              2.30-3.40(9H, m);                                                             3.75(1H, m); 18.30                                                            (1H, s).                                        5-CH.sub.2 CH.sub.2 CH.sub.2 -6                                                          C.sub.2 H.sub.5                                                                       Orange oil 1.15(3H, t); 2.00-                                                            2.40(4H, m); 2.60-                                                            3.12(14H m); 3.63                                                             (1H, m); 7.00(1H, s);                                                         18.20(1H, s).                                   5-CH.sub.2 CH.sub.2 CH.sub.2 -6                                                          n-C.sub.3 H.sub.7                                                                     Orange oil 1.00(3H, t); 1.50(2H,                                                         m); 2.00-2.40(4H, m);                                                         2.60-3.10(14H, m);                                                            3.60(1H, m); 7.00(1H,                                                         s); 18.20(1H, s).                               7-CH.sub.3 -5-                                                                           n-C.sub.3 H.sub.7                                                                     Yellow oil 1.00(3H, t); 1.50(2H,                           CH.sub.2 CH.sub.2 CH.sub.2 -6 m); 2.00-2.40(7H, m);                                                         2.60-3.10(14H, m);                                                            3.60(1H, m); 18.15(1H,                                                        s).                                             5-Br-6,7-  n-C.sub.3 H.sub.7                                                                     Brown oil  1.00(3H, t); 1.50-                              (CH.sub.3).sub.2              3.60(13H, m); 2.24(3H,                                                        s); 2.39(3H, s); 3.80-                                                        4.20(1H, m); 18.30(1H,                                                        s).                                             5,6,7-     n-C.sub.3 H.sub.7                                                                     Orange oil 1.00(3H, t); 1.70(2H,                           (CH.sub.3).sub.3              m); 2.05(2H, m); 2.21                                                         (6H, s); 2.29(3H, s);                                                         2.40-3.20(10H, m);                                                            3.80(1H, m); 18.30                                                            (1H, s).                                        ______________________________________                                    

                  TABLE 8c                                                        ______________________________________                                         ##STR27##                                                                                                  Proton Chemical                                                               Shift δ in ppm                            (X).sub.m + (W).sub.p                                                                   R.sup.3  Appearance (CDCl.sub.3)                                    ______________________________________                                        2,3,4-(CH.sub.3).sub.3                                                                  C.sub.2 H.sub.5                                                                        Yellow oil 1.18(3H, t); 1.80(4H,                                                         m); 2.20(6H, s); 2.30                                                         (3H, s); 2.30-3.50                                                            (10H, m); 3.92(1H, m);                                                        18.20(1H, s).                                   2,3,4-(CH.sub.3).sub.3                                                                  n-C.sub.3 H.sub.7                                                                      Yellow oil 1.00(3H, t); 1.70(6H,                                                         m); 2.10(6H, s); 2.20                                                         (3H, s); 2.20-3.40                                                            (10H, m); 3.95(1H, m);                                                        18.20(1H, s).                                   3,4-(CH.sub.3).sub.2 -                                                                  n-C.sub.3 H.sub.7                                                                      Orange oil 1.00(3H, t); 1.70(6H,                           2-OCH.sub.3                   m); 2.10(3H, s); 2.20                                                         (3H, s); 2.40-3.30                                                            (10H, m); 3.70(3H, s);                                                        3.95(1H, m); 18.25                                                            (1H, s).                                        ______________________________________                                    

                  TABLE 8d                                                        ______________________________________                                         ##STR28##                                                                                                  Proton Chemical                                                               Shift δ in ppm                            (X).sub.m + (W).sub.p                                                                   R.sup.3  Appearance (CDCl.sub.3)                                    ______________________________________                                        H         C.sub.2 H.sub.5                                                                        Yellow solid,                                                                            1.10(3H, t); 1.80(4H,                                              mp 87° C.                                                                         m); 2.60-3.20(11H, m);                                                        7.00-7.20(3H, m);                                                             18.20(1H, s).                                   ______________________________________                                    

                  TABLE 8e                                                        ______________________________________                                         ##STR29##                                                                                                  Proton Chemical                                                               Shift δ in ppm                            (X).sub.m + (W).sub.p                                                                   R.sup.3  Appearance (CDCl.sub.3)                                    ______________________________________                                        2,3,4-(CH.sub.3).sub.3                                                                  n-C.sub.3 H.sub.7                                                                      Orange oil 1.00(3H, t); 1.50-1.80                                                        (8H, m); 2.20-2.30(9H,                                                        m); 2.30-3.40(10H, m);                                                        3.95(1H, m); 18.20(1H,                                                        s).                                             ______________________________________                                    

EXAMPLE 30

The majority of the compounds of the invention were obtained as oils andwere characterized by, and can be identified by their nuclear magneticresonance spectra. For convenience, proton nuclear magnetic resonancespectroscopic (pmr) data and/or melting point data is recorded in Table9 below.

                  TABLE 9                                                         ______________________________________                                        Compound            Proton Chemical Shift                                     No      Appearance  δ in ppm (CDCl.sub.3)                               ______________________________________                                         1      Pale yellow oil                                                                           1.09-1.39(6H, m); 1.90-2.13                                                   (2H, m); 2.68-3.00(11H, m); 4.10                                              (2H, q); 7.04-7.23(3H, m); 14.90                                              (1H, s).                                                   3      Yellow oil  0.92-1.26(6H, m); 2.06(2H, m);                                                2.47-2.95(10H, m); 3.40(1H, m);                                               4.00(2H, q); 7.07-7.25(3H, m);                                                7.45-8.09(5H, m).                                          4      Yellow oil  1.17(3H, t); 2.06(2H, t); 2.68-                                               3.21(11H, m); 4.53(2H, d); 5.36                                               (2H, dofd); 5.91(1H, m); 6.95-                                                7.14(3H, m); 14.95(1H, s).                                 5      Yellow oil  0.98(3H, t); 1.32(3H, t); 1.58                                                (2H, m); 2.06(2H, m); 2.68-3.04                                               (11H, m); 4.10(2H, q); 6.93-7.14                                              (3H, m); 14.06(1H, s).                                     6      Yellow oil  0.97(3H, t); 1.64(2H, m); 2.06                                                (2H, m); 2.75-2.95(10H, m); 3.15                                              (1H, m); 4.52(2H, d); 5.35                                                    (2H, m); 5.89(1H, m); 6.98-7.14                                               (3H, m); 14.77(1H, s).                                     7      Yellow oil  1.08-1.39(6H, m); 1.78(4H, m);                                                2.67-3.09(11H, m); 4.10                                                       (2H, qJ=8Hz); 6.93-6.99(3H, m);                                               15.06(1H, s).                                              8      Yellow oil  1.10-1.40(6H, m); 1.99-2.22                                                   (8H, m); 2.76-3.02(10H, m); 3.56                                              (1H, m); 4.11(2H, q); 6.85                                                    (1H, s); 15.02(1H, s).                                     9      Yellow oil  1.11-1.41(6H, m); 1.96-2.38                                                   (8H, m); 2.38-3.08(10H, m);                                                   4.00-4.24(3H, m); 6.92(1H, s);                                                15.01(1H, s).                                             10      Yellow oil  1.11-1.40(6H, m); 1.92-2.18                                                   (5H, m); 2.33(3H, s); 2.40-3.14                                               (10H, m); 3.64(1H, m); 4.11(2H, q);                                           6.81(1H, s); 14.96(1H, s).                                11      Pale yellow 1.12-1.95(6H, m); 2.03(5H, m);                                    solid       2.30(6H, s); 2.63-3.07(10H, m);                                   mp 99° C.                                                                          4.01-4.21(3H, m); 14.97(1H, s).                           12      Brown oil   1.11-1.40(6H, m); 1.94-2.21                                                   (8H, m); 2.29(3H, s); 2.76-3.00                                               (10H, m); 3.81(1H, m); 4.12(2H, q);                                           15.01(1H, s).                                             13      Yellow oil  1.12-1.41(6H, m); 1.96-2.27                                                   (5H, m); 2.50(3H, s); 2.50-3.05                                               (10H, m); 3.94-4.24(3H, m);                                                   14.96(1H, s).                                             14      Brown oil   1.11-1.40(12H, m); 2.18(6H, s);                                               2.66-3.01(10H, m); 3.50(1H, m);                                               4.11(2H, q); 6.83(1H, s); 14.98                                               (1H, s).                                                  15      Yellow oil  1.12-1.40(12H, m); 2.14(3H, s);                                               2.19(3H, s); 2.29(3H, s); 2.43-                                               2.98(10H, m); 3.95-4.24(3H, m);                                               14.95(1Hs).                                               16      Yellow oil  1.14-1.39(12H, m); 2.70-3.00                                                  (11H, m); 4.10(2H, q); 7.03-7.08                                              (3H, m); 15.02(1H, s).                                    17      Yellow oil  1.12-1.42(6H, m); 2.08-2.23(4H, m);                                           2.37(3H, s); 2.62(3H, s);                                                     2.75(6H, s); 2.86-3.50(8H, m);                                                4.10-4.25(3H, m); 15.20(1H, s).                           18      Bone solid, 1.08-1.40(6H, m); 1.98-3.20(24H,                                  mp 75-77° C.                                                                       m); 4.01-4.24(2H, q); 4.6-4.9                                                 (1H, m); 15.00(1H, s).                                    19      Yellow oil  1.11-1.40(6H, m); 2.40(2H, m);                                                2.31(6H, s); 2.32-2.98(10H, m);                                               3.95-4.24(3H, m); 14.96(1H, s).                           20      Yellow oil  1.04-1.41(9H, m); 2.07(2H, m);                                                2.23(3H, s); 2.33(3H, s); 2.33-                                               2.99(12H, m); 3.85(1H, m); 4.12                                               (2H, q); 14.98(1H, s).                                    21      Orange oil  1.13-1.41(6H, m); 1.97-3.30(18H,                                              m); 3.90-4.10(1H, m); 4.01-4.25                                               (2H, q); 15.01(1H, s).                                    22      Solid,      1.12-1.41(6H, m); 1.95-2.50                                       mp <50° C.                                                                         (12H, m); 2.83-3.05(6H, m);                                                   3.30-4.24(3H, m); 14.96(1H, s).                           23      Yellow oil  1.00(3H, t); 1.32(3H, t); 1.63                                                (2H, m); 2.06(2H, m); 2.33(6H, s);                                            2.33-2.91(10H, m); 4.11(3H, m);                                               15.03(1H, s).                                             24      Cream solid,                                                                              1.00(3H, t); 1.32(3H, t); 1.57                                    mp 131° C.                                                                         (2H, m); 1.90-2.20(2H, m); 2.27                                               (6H, s); 2.27-3.00(8H, m); 3.40-                                              4.23(5H, m); 15.11(1H, s).                                25      Brown oil   1.32(3H, t); 2.00(2H, m); 2.30                                                (6H, s); 2.30-3.40(8H, m); 3.60-                                              4.30(3H, m); 7.20(5H, m); 13.51                                               (1H, s).                                                  26      Yellow oil  1.11-1.41(6H, m); 1.96-2.20(2H, m);                                           2.30(3H, s); 2.44(3H, s);                                                     2.59-3.40(10H, m); 3.60-3.8(1H, m);                                           4.01-4.25(2H, q); 15.09(1H, s).                           27      Yellow oil  1.12-1.41(6H, m); 1.75(4H, m);                                                2.17(3H, s); 2.20(3H, s); 2.35                                                (3H, s); 2.35-2.99(10H, m);                                                   4.00-4.24(3H, m); 14.90(1H, s).                           28      Yellow oil  1.00(3H, t); 1.32(3H, t); 1.75                                                (6H, m); 2.18(3H, s); 2.21(3H, s);                                            2.35(3H, s); 2.35-3.40(10H, m);                                               3.90-4.23(3H, m); 15.07(1H, s).                           29      Yellow oil  1.00(3H, t); 1.32(3H, t); 1.69                                                (8H, m); 2.23(3H, s);                                                         2.26(3H, s); 2.30(3H, s); 2.30-                                               3.00(10H, m); 3.90-4.24(3H, m);                                               15.07(1H, s).                                             30      Yellow oil  1.00(3H, t); 1.32(3H, t); 1.56                                                (6H, m); 2.13(3H, s);                                                         2.21(3H, s); 2.21-3.02(10H, m);                                               3.95(4H, m); 4.10(2H, q); 15.04                                               (1H, s).                                                  31      Pale orange Not recorded                                                      solid, mp                                                                     270° C.                                                                (decomp.)                                                             32      Yellow oil  1.12-1.41(6H, m); 1.61(2H, m);                                                1.96-2.27(8H, m); 2.50(3H, s);                                                2.50-3.06(10H, m); 3.94-4.24                                                  (3H, m); 7.45-7.64(3H, m); 7.98-                                              8.09(2H, m).                                              33      White solid Not recorded                                                      mp >250° C.                                                            (decomp.)                                                             34      Yellow oil  1.00(3H, t); 1.33(3H, t); 1.65                                                (2H, m); 1.97-2.25(8H, m); 2.25-                                              3.03(10H, m); 3.60(1H, m); 4.11                                               (2H, q); 15.17(1H, s).                                    35      Cream solid,                                                                              Not recorded                                                      mp >260° C.                                                    36      Cream solid,                                                                              Not recorded                                                      mp 240° C.                                                     37      Yellow oil  0.93(3H, t); 1.27(3H, t); 1.57                                                (2H, m); 2.11(2H, m); 2.15(3H, s);                                            2.20(6H, s); 2.30(3H, s); 2.37-                                               3.17(10H, m); 3.51-4.26(3H, m).                           38      Yellow oil  0.87(3H, t); 1.19(3H, t); 1.40                                                (2H, m); 2.00(2H, m); 2.21(6H, s);                                            2.28(3H, s); 2.46(3H, s); 2.46-                                               3.95(10H, m); 3.95-4.19(3H, m);                                               7.52(4H, m).                                              39      Yellow oil  1.01(3H, t); 1.60(2H, m); 2.10                                                (2H, m); 2.21(6H, s); 2.29(3H, s);                                            2.29-3.40(10H, m); 3.70(1H, m);                                               4.64(2H, s); 5.81(2H, m); 13.90                                               (1H, s).                                                  40      Green solid,                                                                              Not recorded                                                      mp 212° C.                                                             (decomp.)                                                             41      Pale green solid,                                                                         Not recorded                                                      mp 231° C.                                                             (decomp.)                                                             42      Yellow oil  0.82-1.17(6H, m); 1.60(2H, m);                                                2.05(2H, m); 2.21(6H, s); 2.34                                                (3H, s); 2.38-3.47(10H, m); 3.94-                                             4.01(3H, m); 8.26(4H, m).                                 43      Yellow oil  0.83-1.06(15H, m); 1.18-1.60                                                  (21H, m); 1.97(2H, m); 2.19(6H, s);                                           2.28(3H, s); 2.81-3.15(18H, m);                                               3.60-4.21(3H, m).                                         44      Yellow oil  0.99(3H, t); 1.58(2H, m); 2.02                                                (2H, m); 2.21(6H, s); 2.29(3H, s);                                            2.29-3.10(10H, m); 3.74(1H, m);                                               4.11-4.20(1H, m); 4.36-4.51(2H,                                               4.89-4.98(1H, m); 14.13(1H, s).                           45      Yellow oil  1.32(3H, t); 2.00(2H, m); 2.22                                                (6H, s); 2.34(3H, s); 2.40-3.20                                               (8H, m); 3.90- 4.30(3H, m); 7.40                                              (5H, m); 13.51(1H, s).                                    46      Yellow oil  1.10-1.39(9H, m); 2.68-3.08(12H,                                              m); 4.10(2H, q); 7.02-7.24(3H, m);                                            14.99(1H, s).                                             47      Yellow oil  1.11-1.36(12H, m); 1.85(2H, m);                                               2.26(9H, s); 2.26-3.06(8H, m);                                                3.99-4.23(3H, m); 14.94(1H, s).                           48      Yellow oil  1.03-1.98(15H, m); 2.06-2.27                                                  (10H, m); 2.27-3.06(8H, m);                                                   3.79-4.24(3H, m); 14.94(1H, s).                           49      Yellow oil  0.92-1.59(15H, m); 1.75(2H, m);                                               2.06-2.27(10H, m); 2.27-3.01                                                  (8H, m); 3.78-4.23(3H, m); 15.06                                              (1H, s).                                                  50      Yellow oil  0.92-1.78(6H, m); 1.32(3H, t);                                                1.50-1.80(3H, m); 2.17(3H, s);                                                2.31(3H, s); 2.34(3H, s); 2.17-                                               3.40(10H, m); 3.70-4.24(3H, m);                                               15.08(1H, s).                                             51      Yellow oil  1.00(3H, t); 1.16(3H, d); 1.32                                                (3H, t); 1.58(2H, m); 2.16(3H, s);                                            2.28(6H, s); 2.28-3.12(11H, m);                                               3.60-4.23(3H, m); 15.09(1H, s).                           52      Pale yellow oil                                                                           1.14-1.41(12H, m); 2.17(3H, s);                                               2.19(3H, s); 2.28(3H, s); 2.30-                                               3.00(10H, m); 3.80(1H, m); 4.12                                               (2H, q); 15.01(1H, s).                                    53      Yellow oil  1.00-1.40(12H, m); 1.60(2H, m);                                               2.16(3H, s); 2.19(3H, s); 2.28                                                (3H, s); 2.28-3.30(10H, m); 3.70                                              (1H, m); 4.11(2H, q); 15.13(1H, s).                       54      Yellow oil  1.11-1.41(12H, m); 1.84(2H, t);                                               2.16(3H, s); 2.19(3H, s); 2.33                                                (3H, s); 2.33-2.98(8H, m); 3.98-                                              4.17(3H, m); 14.90(1H, s).                                55      Yellow oil  0.92-1.40(10H, m); 1.60(2H, m);                                               2.20-3.17(19H, m); 3.50-3.85                                                  (1H, m); 4.11(2H, q); 15.14(1H, s).                       56      Pale yellow oil                                                                           0.92-1.40(9H, m); 1.60(2H, m);                                                2.19(3H, s); 2.24(3H, s); 2.29                                                (3H, s); 2.19-3.29(11H, m); 3.90                                              (1H, m); 4.11(2H, q); 15.09(1H, s).                       57      Yellow oil  1.11-1.41(6H, m); 1.98-2.21                                                   (4H, m); 2.77-3.00(14H, m); 3.58                                              (1H, m); 4.12(2H, q); 7.04(1H, s);                                            15.04(1H, s).                                             58      Yellow oil  1.00(3H, t); 1.32(3H, t); 1.57                                                (2H, m); 2.06(4H, m); 2.77-3.00                                               (14H, m); 3.60(1H, m); 4.11(2H, q);                                           7.04(1H, s); 15.14(1H, s).                                59      Yellow oil  1.00(3H, t); 1.32(3H, t); 1.58                                                (2H, m); 2.07-2.28(7H, m); 2.73-                                              3.03(14H, m); 3.40(1H, m); 4.11                                               (2H, q); 15.12(1H, s).                                    60      Yellow oil  1.00(3H, t); 1.32(3H, t); 1.40-                                               3.55(15H, m); 2.24(3H, s); 2.39                                               (3H, s); 4.11(2H, q); 15.16(1H, s)                        61      Yellow oil  1.01(3H, t); 1.32(3H, t); 1.61                                                (2H, m); 2.06(2H, m); 2.21(6H, s);                                            2.29(3H, s); 2.75-3.10(10H, m);                                               3.73(1H, m); 4.11(2H, q); 15.13                                               (1H, s).                                                  ______________________________________                                    

EXAMPLE 31

This non-limiting Example illustrates the preparation of formulations ofthe compounds of the invention.

a) Emulsifiable Concentrate

Compound No 61 was dissolved in toluene containing 7% v/v "Teric" N13and 3% v/v "Kemmat" SC15B to give an emulsifiable concentrate which maybe diluted with water to the required concentration to give an aqueousemulsion which may be applied by spraying.

("Teric" is a Trade Mark and "Teric" N13, is a product of ethoxylationof nonylphenol; "Kemmat" is a Trade Mark and "Kemmat" SC15B is aformulation of calcium dodecylbenzenesulfonate.)

b) Aqueous Suspension

Compound No 61 (5 parts by weight) and "Dyapol" PT (1 part by weight)was added to an aqueous solution (94 parts by weight) of "Teric" N8 andthe mixture was ball milled to produce a stable aqueous suspension whichmay be diluted with water to the required concentration to give anaqueous suspension which may be applied by spraying. ("Dyapol" is aTrade Mark and "Dyapol" PT is an anionic suspending agent; "Teric" N8 isa product of ethoxylation of nonylphenol.)

c) Emulsifiable Concentrate

Compound No 61 (10 parts by weight), "Teric" N13 (5 parts by weight) and"Kemmat" SC15B (5 parts by weight) were dissolved in "Solvesso" 150 (80parts by weight) to give an emulsifiable concentrate which may bediluted with water to the required concentration to give an aqueousemulsion which may be applied by spraying. ("Solvesso" is a Trade Markand "Solvesso" 150 is a high boiling point aromatic petroleum fraction.)

d) Dispersible Powder

Compound No 61 (10 parts by weight), "Matexil" DA/AC (3 parts byweight), "Aerosol" OT/B (1 part by weight) and china clay 298 (86 partsby weight) were blended and then milled to give a powder compositionhaving a particle size below 50 microns. ("Matexil" is a Trade Mark and"Matexil" DA/AC is the disodium salt of a naphthalenesulfonicacid/formaldehyde condensate; "Aerosol" is a Trade Mark and "Aerosol"OT/B is a formulation of the dioctyl ester of sodium sulfosuccinicacid.)

e) High Strength Concentrate

Compound No 61 (99 parts by weight), silica aerogel (0.5 parts byweight) and synthetic amorphous silica (0.5 parts by weight) wereblended and ground in a hammer-mill to produce a powder having aparticle size less than 200 microns.

f) Dusting Powder

Compound No 61 (10 parts by weight), attapulgite (10 parts by weight)and pyrophyllite (80 parts by weight) were thoroughly blended and thenground in a hammer-mill to produce a powder of particle size less than200 microns.

Emulsifiable concentrates and/or suspensions of the compounds of theinvention were prepared essentially as described in part a), b) or c)above and then diluted with water, optionally containing a surfaceactive agent and/or oil, to give aqueous compositions of the requiredconcentration which were used, as described in Examples 32 and 33, inthe evaluation of the pre-emergence and post-emergence herbicidalactivity of the compounds.

EXAMPLE 32

The pre-emergent herbicidal activity of the compounds of the inventionformulated as described in Example 31 was assessed by the followingprocedure:

The seeds of the test species were sown in rows 2 cm deep in soilcontained in seed boxes. The monocotyledonous plants and thedicotyledonous plants were sown in separate boxes and after sowing thetwo boxes were sprayed with the required quantity of a composition ofthe invention. Two duplicate seed boxes were sprayed with the requiredquantity of a composition of the invention. Two duplicate seed boxeswere prepared in the same manner but were not sprayed with a compositionof the invention and were used for comparison purposes. All the boxeswere placed in a glass house, lightly watered with an overhead spray toinitiate germination and then sub-irrigated as required for optimumplant growth. After three weeks the boxes were removed from the glasshouse and the effect of the treatment was visually assessed. The resultsare presented in Table 10 where the damage to plants is rated on a scaleof from 0 to 5 where 0 represents from 0 to 10% damage, 1 representsfrom 11 to 30% damage, 2 represents from 31 to 60% damage, 3 representsfrom 61 to 80% damage, 4 represents from 81 to 99% damage and 5represents 100% kill. A dash (--) means that no experiment was carriedout.

The names of the test plants are as follows:

    ______________________________________                                               Wh          Wheat                                                             Ot          Wild Oats                                                         Rg          Ryegrass                                                          Jm          Japanese millet                                                   P           Peas                                                              Ip          Ipomea                                                            Ms          Mustard                                                           Sf          Sunflower                                                  ______________________________________                                    

                  TABLE 10                                                        ______________________________________                                        PRE-EMERGENCE HERBICIDAL ACTIVITY                                             Com-  APPLI-                                                                  pound CATION     TEST PLANT                                                   No    Rate (kg/ha)                                                                             Wh     Ot   Rg   Jm   P   Ip  Ms  Sf                         ______________________________________                                         1    2.0        0      0    5    5    0   0   0   0                           1    0.5        0      0    4    4    0   0   0   0                           3    5.0        3      3    5    5    0   0   0   0                           3    2.0        0      3    5    5    0   0   0   0                           3    0.5        0      0    4    3    0   0   0   0                           4    1.0        0      0    5    4    0   0   0   0                           4    0.25       0      0    0    0    0   0   0   0                           5    1.0        0      0    5    3    0   0   0   0                           5    0.25       0      0    0    0    0   0   0   0                           6    1.0        0      0    4    3    0   0   0   0                           6    0.25       0      0    0    0    0   0   0   0                           7    1.0        0      0    4    5    0   0   0   0                           7    0.25       0      0    0    0    0   0   0   0                           8    1.0        1      4    5    5    0   0   0   0                           8    0.25       0      2    5    5    0   0   0   0                           9    0.25       0      0    5    5    0   0   0   0                           9    0.125      0      0    5    5    0   0   0   0                          11    0.25       0      0    5    5    0   0   0   0                          11    0.125      0      0    5    5    0   0   0   0                          12    1.0        0      0    5    5    0   0   0   0                          12    0.25       0      5    5    5    0   0   0   0                          13    0.25       0      0    5    4    0   0   0   0                          13    0.125      0      0    5    2    0   0   0   0                          14    0.5        1      4    4    5    0   0   0   0                          14    0.125      0      0    3    3    0   0   0   0                          15    0.5        0      4    5    5    0   0   0   0                          15    0.125      0      0    4    5    5   0   0   0                          16    0.5        0      0    2    1    0   0   0   0                          17    0.5        3      4/5  5    5    0   0   0   0                          17    0.125      0      0    5    4    0   0   0   0                          18    0.5        0      0    4    4/5  0   0   0   0                          19    0.5        0      1    3    5    0   0   0   0                          19    0.125      0      0    2    3    0   0   0   0                          20    0.5        0      4    5    5    0   0   0   0                          20    0.125      0      0    5    1    0   0   0   0                          22    0.25       0      2    4    5    0   0   0   0                          23    0.25       0      0    1    4    0   0   0   0                          24    1.0        0      4    5    5    0   0   0   0                          27    0.5        0      1    4    5    0   0   0   0                          30    1.0        0      5    5    5    0   0   0   0                          31    1.0        5      5    5    5    0   0   0   0                          31    0.25       0      4/5  0    0    0   0   0   0                          32    1.0        3      3    4    4    0   0   0   0                          33    1.0        0      1    0    5    0   0   0   0                          46    0.5        0      0    3    4    0   0   0   0                          47    0.25       0      1    5    5    0   0   0   0                          48    1.0        4      4    5    5    0   0   0   0                          48    0.25       0      0    3    4    0   0   0   0                          49    1.0        0      0    5    5    0   0   0   0                          50    1.0        5      5    5    5    0   0   0   0                          50    0.25       1      3    4/5  5    0   0   0   0                          51    1.0        0      4    4    5    0   0   0   0                          56    1.0        1      5    5    5    0   0   0   0                          56    0.25       0      3    4    4    0   0   0   0                          58    0.5        0      0    3    5    0   0   0   0                          60    1.0        0      4/5  5    5    0   0   0   0                          ______________________________________                                    

EXAMPLE 33

The post-emergent herbicidal activity of the compounds of the inventionformulated as described in Example 31 was assessed by the followingprocedure.

The seeds of the test species were sown in rows 2 cm deep in soilcontained in seed boxes. The monocotyledonous plants and thedicotyledonous plants were sown in separate seed boxes in duplicate. Thefour seed boxes were placed in a glass house, lightly watered with anoverhead spray to initiate germination and then sub-irrigated asrequired for optimum plant growth. After the plants had grown to aheight of about 10 to 12.5 cm one box of each of the monocotyledonousplants and the dicotyledonous plants was removed from the glass houseand sprayed with the required quantity of a composition of theinvention. After spraying the boxes were returned to the glass house fora further 3 weeks and the effect of treatment was visually assessed bycomparison with the untreated controls. The results are presented inTable 11 where the damage to plants is rated on a scale of from 0 to 5where 0 represents from 0 to 10% damage, 1 represents from 11 to 30%damage, 2 represents from 31 to 60% damage, 3 represents from 61 to 80%damage, 4 represents from 81 to 99% damage and 5 represents 100% kill. Adash (--) means that no experiment was carried out.

The names of the test plants are as follows:

    ______________________________________                                               Wh          Wheat                                                             Ot          Wild Oats                                                         Rg          Ryegrass                                                          Jm          Japanese Millet                                                   P           Peas                                                              Ip          Ipomea                                                            Ms          Mustard                                                           Sf          Sunflower                                                  ______________________________________                                    

                  TABLE 11                                                        ______________________________________                                        POST-EMERGENCE HERBICIDAL ACTIVITY                                            Com-  APPLI-                                                                  pound CATION     TEST PLANT                                                   No    Rate (kg/ha)                                                                             Wh     Ot   Rg   Jm   P   Ip  Ms  Sf                         ______________________________________                                         1    2.0        3      5    5    5    0   0   0   0                           1    0.5        0      5    5    5    0   0   0   0                           3    5.0        0      5    5    5    0   0   0   0                           3    2.0        0      5    5    5    0   0   0   0                           3    0.5        0      3    4    5    0   0   0   0                           4    1.0        1      5    5    5    0   0   0   0                           4    0.25       0      4    5    5    0   0   0   0                           5    1.0        3      5    5    5    0   0   0   0                           5    0.25       0      5    5    5    0   0   0   0                           6    1.0        3      5    5    5    0   0   0   0                           6    0.25       0      5    5    5    0   0   0   0                           7    1.0        0      5    5    5    0   0   0   0                           7    0.25       0      4    5    5    0   0   0   0                           8    1.0        5      5    5    5    0   0   0   0                           8    0.25       1      5    5    5    0   0   0   0                           9    0.25       3      5    5    5    0   0   0   0                           9    0.125      2      5    5    5    0   0   0   0                          10    0.25       2      5    5    5    0   0   0   0                          10    0.125      0      5    5    5    0   0   0   0                          11    0.25       4      5    5    5    0   0   0   0                          11    0.125      3      5    5    5    0   0   0   0                          12    1.0        3      5    5    5    0   0   0   0                          12    0.25       0      3    5    5    0   0   0   0                          13    0.25       3      5    5    5    0   0   0   0                          13    0.125      0      5    5    5    0   0   0   0                          14    0.5        5      5    5    5    0   0   0   0                          14    0.125      4      4    3    5    0   0   0   0                          15    0.5        5      5    5    5    0   0   0   0                          15    0.125      4      5    5    5    0   0   0   0                          16    0.5        0      3    5    5    0   0   0   0                          16    0.125      0      0    5    5    0   0   0   0                          17    0.5        4/5    5    5    5    0   0   0   0                          17    0.125      3      5    5    5    0   0   0   0                          18    0.5        0      0    4    5    0   0   0   0                          18    0.125      0      0    2    5    0   0   0   0                          19    0.5        4      5    5    5    0   0   0   0                          19    0.125      2      4    5    5    0   0   0   0                          20    0.5        4      5    5    5    0   0   0   0                          20    0.125      3      4    5    5    0   0   0   0                          21    0.125      0      0    2    4    0   0   0   0                          22    0.25       0      3/4  5    5    0   0   0   0                          22    0.0625     0      3/4  4/5  5    0   0   0   0                          23    0.25       0      3/4  4/5  5    0   0   0   0                          24    1.0        0      5    5    5    0   0   0   0                          24    0.25       0      4    2    3    0   0   0   0                          26    0.125      0      1    0    5    0   0   0   0                          27    0.5        3      4/5  5    5    0   0   0   0                          27    0.125      0      3    4    5    0   0   0   0                          28    0.25       0      0    4    4    0   0   0   0                          29    0.25       0      0    3    1    0   0   0   0                          30    1.0        3/4    5    5    5    0   0   0   0                          30    0.25       0      2    0    0    0   0   0   0                          31    1.0        3      5    5    5    0   0   0   0                          31    0.25       0      5    5    5    0   0   0   0                          31    0.0625     0      5    4    5    0   0   0   0                          32    1.0        3      5    5    5    0   0   0   0                          32    0.25       0      5    0    0    0   0   0   0                          33    1.0        0      5    5    5    0   0   0   0                          33    0.25       0      5    4/5  5    0   0   0   0                          37    1.0        3      5    5    5    0   0   0   0                          37    0.25       0      5    4    5    0   0   0   0                          46    0.5        4      1    5    5    0   0   0   0                          46    0.125      3      2    5    5    0   0   0   0                          47    0.25       0      0    3    4    0   0   0   0                          48    1.0        1      4/5  5    5    0   0   0   0                          48    0.25       0      1    0    2    0   0   0   0                          49    1.0        1      4/5  4    5    0   0   0   0                          49    0.25       0      1    0    2    0   0   0   0                          50    1.0        5      5    5    5    0   0   0   0                          50    0.25       3      5    5    5    0   0   0   0                          51    1.0        5      5    5    5    0   0   0   0                          51    0.25       4      5    5    5    0   0   0   0                          51    0.0625     2      5    5    5    0   0   0   0                          52    0.125      0      0    0    2    0   0   0   0                          53    0.25       0      0    0    0    0   0   0   0                          54    0.25       0      0    3    4    0   0   0   0                          55    1.0        0      3/4  3    3    0   0   0   0                          55    0.25       0      2    1    2    0   0   0   0                          56    1.0        1      5    5    5    0   0   0   0                          56    0.25       0      5    3    4    0   0   0   0                          57    0.5        0      0    4/5  5    0   0   0   0                          58    0.5        0      2    4    5    0   0   0   0                          59    0.25       0      4    3    5    0   0   0   0                          60    1.0        1      5    5    5    0   0   0   0                          60    0.25       0      5    5    5    0   0   0   0                          61    0.125      0      4    4    5    0   0   0   0                          61    0.031      0      4    3    4    0   0   0   0                          ______________________________________                                    

EXAMPLE 34

This Example illustrates the selective herbicidal activity of compoundsof the invention.

The compounds were formulated for test by mixing an appropriate amountwith 5 ml of an emulsion prepared by diluting 160 ml of a solutioncontaining 21.8 g per liter of "Span" 80 and 78.2 g per liter of "Tween"20 in methylcyclohexanone to 500 ml with water. "Span" 80 is a TradeMark for a surface-active agent comprising sorbitan monolaurate. "Tween"20 is a Trade Mark for a surface-active agent comprising a condensate ofsorbitan monolaurate with 20 molar proportions of ethylene oxide. Each 5ml emulsion containing a test compound was then diluted to 40 ml withwater and sprayed on to young pot plants (post-emergence test) of thespecies named in Tables 12 and 13 below. Damage to test plants wasassessed after 26 days on a scale of 0 to 9 where 0 is 0 to 10% damageand 9 is complete kill. The degree of herbicidal damage was assessed bycomparison with untreated control plants and the results are given inTables 12 and 13 below. A dash (--) means that no experiment was carriedout.

                                      TABLE 12                                    __________________________________________________________________________    POST-EMERGENCE HERBICIDAL ACTIVITY                                            Compound                                                                            APPLICATION                                                                            TEST PLANT                                                     No    Rate (kg/ha)                                                                           Mz Rc                                                                              Sy                                                                              Ct                                                                              Sg                                                                              Ec                                                                              Dg St                                                                              Sh                                                                              Pm Sf                                                                              Ei                                    __________________________________________________________________________    53    0.02     1  2 --                                                                              --                                                                              1 9 8  7 1 4  7 8                                     61    0.025    4  0 --                                                                              --                                                                              6 9 9  5 2 3  7 9                                     __________________________________________________________________________

The names of the test plants were as follows:

    ______________________________________                                        Mz               Maize                                                        Rc               Rice                                                         Sy               Soyabean                                                     Ct               Cotton                                                       Sg               Sorghum                                                      Ec               Echinochloa crus-gali                                        Dg               Digitaria sanguinalis                                        St               Setaria viridis                                              Sh               Sorghum halepense                                            Pm               Panicum maximum                                              Sf               Setaria faberii                                              Ei               Eleusine indica                                              ______________________________________                                    

                  TABLE 13                                                        ______________________________________                                        POST-EMERGENCE HERBICIDAL ACTIVITY                                            Com-  APPLI-                                                                  pound CATION      TEST PLANT                                                  No    Rate (kg/ha)                                                                              Ww     Br  Av   Al  Bs   Ll  St  Ap                         ______________________________________                                         1    0.12        0      --  8    7   --   --  7   --                          9    0.06        2      --  8    9   4    8   8   8                          10    0.08        0      2   9    9   0    9   8   9                          10    0.06        0      --  9    8   0    9   7   9                          11    0.06        2      --  8    9   1    8   9   9                          ______________________________________                                    

The names of the test plants were as follows:

    ______________________________________                                        Ww              Winter wheat                                                  Br              Spring barley                                                 Av              Avena fatua                                                   Al              Alopecurus myosuroides                                        Bs              Bromus sterilis                                               Ll              Lolium parenne                                                Ap              Apera spica venti                                             St              Setaria viridis                                               ______________________________________                                    

We claim:
 1. A compound of formula XIII ##STR30## wherein W, which maybe the same or different, are selected from the group consisting of C₁to C₆ alkyl, C₂ to C₆ alkenyl and C₂ to C₆ alkynyl;X, which may be thesame or different, are selected from the group consisting of: halogen;nitro; cyano; C₁ alkyl; C₁ to C₆ alkyl substituted with a substituentselected from the group consisting of halogen, nitro, hydroxy, C₁ to C₆alkoxy and C₁ to C₆ alkylthio; C₂ to C₆ alkenyl; C₂ to C₆ alkynyl;hydroxy; C₁ to C₆ alkoxy; C₁ to C₆ alkoxy substituted with a substituentselected from halogen and C₁ to C₆ alkoxy; C₂ to C₆ alkenyloxy; C₂ to C₆alkynyloxy; C₂ to C₆ alkanoyloxy; (C₁ to C₆ alkoxy)-carbonyl; C₁ to C₆alkylthio; C₁ to C₆ alkylsulfinyl; C₁ to C₆ alkylsulfonyl; sulfamoyl;N-(C₁ to C₆ alkyl)-sulfamoyl; N,N-di(C₁ to C₆ alkyl)sulfamoyl;benzyloxy; substituted benzyloxy wherein the benzene ring is substitutedwith from one to three substituents selected from the group consistingof halogen, nitro, C₁ to C₆ alkyl, C₁ to C₆ alkoxy and C₁ to C₆haloalkyl; the group NR⁸ R⁹ wherein R⁸ and R⁹ are independently selectedfrom the group consisting of hydrogen; C₁ to C₆ alkyl, C₂ to C₆alkanoyl, benzoyl and benzyl; the groups formyl and C₂ to C₆ alkanoyland the oxime, imine and Schiff base derivatives thereof; and the group--(CH₂)_(g) -- which bridges two adjacent carbon atoms of the benzenering and wherein q is an integer selected from 2 to 5; R³ is selectedfrom the group consisting of: C₁ to C₆ alkyl; C₁ to C₆ fluoroalkyl; C₂to C₆ alkenyl; C₂ to C₆ alkynyl; and phenyl; p is zero or an integerselected from 1 to 4; n is zero or an integer selected from 1 to 3; m iszero or an integer selected from 1 to
 3. 2. A compound according toclaim 1, said compound being2-propanoly-3-hydroxy-5-(5,6,7-trimethylindan-4-yl)cyclohex-2-en-1-one.